Cyclopropylboronic compounds, method for preparing same and use thereof

ABSTRACT

Cyclopropylboronic compounds, the preparation process thereof and the use thereof.

A subject of the present invention is cyclopropylboronic compounds, thepreparation process thereof and the use thereof.

The cyclopropane unit is present in numerous natural products (terpenes,steroids, polycetides, pheromones, metabolites of fatty acids, unusualamino acids) having very varied biological activities (antibiotic,antiviral, antifungal, antitumour, neuromediator, insecticide,regulation of plant growth, ripening of fruit).

Chrysanthemic acid and the pyrethrins, insecticides isolated from theflower Chrysanthemum cinerariaefolium, can be mentioned as examples ofnatural bioactive cyclopropanes:

The electronic and steric properties of cyclopropane, in particular itsconformational rigidity which makes it possible to orientate thefunctional groups in space in a perfectly defined manner, make it astructural unit that is particularly important and useful in medicinalchemistry.

The cyclopropane unit, in particular substituted by a heteroatom(nitrogen or oxygen) is found in numerous medicinal products currentlyon the market, and candidate medicinal products in development, forexample Tranylcypromine, Trovafloxacin, Tasimelteon and anti-viralsagainst hepatitis C, in particular MR 200 (J. Med. Chem. 2011, 54(10),3669), Simeprevir, Danoprevir, Asunaprevir, MK 5172, Sovaprevir andVanipevir.

The cyclopropanic compounds also constitute important intermediates inorganic synthesis. According to the nature of the substituents and theirelectronic properties, the ring with three members can be opened bythermal, photochemical reactions, promoted by electrophiles,nucleophiles, radicals or catalyzed by organometallic complexes, themotive force of which is the release of the ring strain.

In view of the importance of this structural element, numerous synthesesof cyclopropanes have been published. The majority of the reactionsforming a cyclopropyl ring involve on the Simmons-Smith reaction, theCorey-Chaikovski reaction or the addition of a carbene formed from adiazoic compound.

However, these reactions do not allow the direct and convergentintroduction of a cyclopropyl unit onto a molecule of interest.

Within the context of organometallic couplings, theorganotrifluoroborates have numerous advantages as reagents compared tothe boronic acids and the esters of said acids: saidorganotrifluoroborates are tetravalent “ate” complexes havingexceptional stability in air, humidity the nucleophilic compounds. Thevast majority can be stored indefinitely at ambient temperature withoutspecific precautions. Finally, despite this stability, theorganotrifluoroborate derivatives have a very high reactivity over awide range of reactions and particularly the organometallic couplingscatalyzed by a transition metal.

Thus, one of the objectives of the present invention consists ofproviding functionalized cyclopropyl trifluoroborate compounds.

Another objective of the invention consists of preparing said compoundsby a simple and rapid process.

Another objective of the invention is the use of said functionalizedcyclopropyl trifluoroborate compounds in an organometallic couplingreaction catalyzed by a transition metal in order to introduce afunctionalized cyclopropyl unit into a molecule of interest.

As a result, a subject of the invention is a process for the preparationof a compound corresponding to the following formula (I):

in which:

X represents a substituted boron atom chosen from the group comprisingB(OH)₂, B(OR)₂, BF₃M, B(OR′)₃M in which:

-   -   R is an alkyl group comprising 1 to 14 carbon atoms or an aryl        group, optionally substituted, or is such that (OR)₂ forms a        ring between the two oxygen atoms, (OR)₂ being in particular        chosen from the group comprising the bivalent radicals deriving        from diols, such as O—CH₂—CH₂—O, O—CH₂—CH₂—CH₂—O,        O—CH₂—C(CH₃)₂—CH₂—O, O—C(CH₃)₂—CH₂—CH₂—C(CH₃)₂—O,        O—CH(CH₃)—CH₂—CH₂—CH(CH₃)—O, O—CH(Ph)-CH(Ph)-O,        O—CH(CH₃)—CH₂—C(CH₃)₂—O, O-o-Ph-O, O—CH₂—CH₂—NH—CH₂—CH₂—O,        O—CH₂—CH₂—N(CH₂—CH₂—CH₂—CH₃)—CH₂—CH₂—O, O—CH(COOH)—CH(COOH)—O        and its esters, and the bivalent radicals deriving from diacids,        such as OCO—CH₂—N(CH₃)—CH₂—COO,    -   R′ is an alkyl group comprising 1 to 14 carbon atoms or is such        that:        -   (OR′)₃ forms a ring between two of the oxygen atoms, (OR′)₃            then being in the form OR′(OR)₂, where R′ is an alkyl group            comprising 1 to 14 carbon atoms and (OR)₂ is as defined            above, or        -   (OR′)₃ forms a bicycle between the three oxygen atoms,            (OR′)₃ being in particular chosen from the group comprising            the trivalent radicals deriving from triols, such as            H₃C—C—(CH₂—O)₃,    -   M represents the lithium Li⁺ ion, the sodium Na⁺ ion, the        potassium K⁺ ion, the caesium Cs⁺ ion, the ammonium        R^(c)R^(d)R^(e)R^(f)N⁺ ion where R^(c)R^(d)R^(e)R^(f) are chosen        from H or a saturated carbon-containing chain comprising in        particular 1 to 6 carbon atoms chosen independently of one        another, and in particular X represents B(OH)₂, B(OR)₂ or BF₃K,

R₁, R₄ and R₅, identical or different, are chosen from the groupconstituted by:

1. H

2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;R₁ and R₄, or R₁ and R₅ being able to form a ring with 5, 6, or 7members optionally comprising a heteroatom chosen from oxygen, nitrogenand sulphur, said ring being able to be substituted;

R₂ is chosen from the group constituted by the groups being able to berepresented by R₁, R₄ or R₅, as well as —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CONH—SO₂—R^(a), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, —CH₂—NH—COR′, —OH,—OR^(a), —OZ′, —NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂,

in which Z and Z₂ represent a protective group of an amine function, andZ′ represents a protective group of an alcohol function, andin which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;

when W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CH₂OH, —CH₂OR^(a),—CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)H, —CR^(b)R^(b′)OR^(a),—CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, said process comprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined above, W₁ being chosen from the group        constituted by —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), and        —CONR^(a)R^(b),        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄, R₅ and M are as defined above,        -   in the presence of a catalyst containing a transition metal,            in order to obtain a compound of the following formula:

-   -   in which R₁, R₂, R₄, R₅, W₁ and M are as defined above,        if W is different from W₁ and/or X is different from MF₃B, said        process also comprising the following steps:    -   a step of conversion of W₁ to W making it possible to obtain

in particular, when W₁=COOR^(a) and W=CHO, by reduction in order to formthe corresponding alcohol, then oxidation of said alcohol, whenW₁=—COOR^(a) and W=CH₂OH or —CH₂OR^(b), by the formation of an aldehydeas described previously, then by reduction of said aldehyde and optionalalkylation, when W₁=—COR^(a) and W=—CHR^(a)OH, —CHR^(a)OR^(b), byreduction then optional alkylation of the alcohol obtained, whenW₁=—COR^(a) and W=CR^(a)R^(b)OH or —CR^(a)R^(b)OR^(b′) by addition of aGrignard reagent then optional alkylation of the alcohol obtained, whenW₁=—CONH₂, —CONHR^(a) or —CONR^(a)R^(b) and W=—CH₂NH₂, —CH₂NHR^(a),—CH₂NR^(a)R^(b), —CH₂NHZ or —CH₂—NH—COR^(a), by reduction then optionalprotection by Z of the amine obtained or optional reaction with the acidchloride R^(a)COCl, when W₁=—CONH₂ and W=—CONHSO₂R^(a), by the action ofsulphonyl chloride ClSO₂R^(a) on the amide,

and

-   -   a step of conversion of —BF₃M to —X making it possible to obtain

in particular, when X=B(OH)₂, by basic or acid hydrolysis, or by passingvia a dihalogenoborane, more particularly a dichloroborane, whenX=B(OR)₂, by passing via X=B(OH)₂ as described previously then by theaction of an alcohol, in particular an alcohol of formula ROH, a diol ora triol, or by passing via a dihalogenoborane, more particularly adichloroborane, then by the action of an alcohol, in particular analcohol of formula ROH, a diol or a triol,

or

-   -   a step of conversion of —BF₃M to —X making it possible to obtain

and

-   -   a step of conversion of W₁ to W making it possible to obtain

when W represents a functional group chosen from —OH, —OR^(a), —OZ′,—NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂, in particular from —OH,—OR^(a) and —OZ′, said process comprising:

-   -   the treatment of a compound of the following formula:

in which R₂ is as defined above,and in which W₂ represents a functional group chosen from —OR^(a), —OZ′,—NR^(a)R^(b) and —NZZ₂, in particular from —OR^(a) and —OZ′, Y being ahalide, in particular —Br, Y′ being a halide, in particular —Br, or H,by:

-   -   a strong base, in particular an alkyl lithium, more particularly        n-butyllithium or sec-butyllithium, then    -   a compound of formula X″—B(OR)₂, R being as defined above, X″        representing H, an O-alkyl group comprising 1 to 14 carbon atoms        or an O-aryl group, optionally substituted,        in order to obtain a compound of the following formula:

in which R, R₂ and W₂ are as defined above,or

a reaction of the Simmons-Smith type starting from a compound of thefollowing formula:

in which R₁ and R₂ are as defined previously, W₂ representing afunctional group chosen from —OR^(a), —OZ′, —NR^(a)R^(b) and —NZZ₂, inparticular from —OR^(a) and —OZ′, X′ representing B(OR)₂ or BF₃M, inparticular B(OR)₂, in which R and M are as defined previously,in order to obtain a compound of the following formula:

in which R₁, R₂, X′ and W₂ are as defined above,

if W represents —OH or —NH₂, and/or X is different from B(OR)₂, saidprocess also comprising the following steps, R₁ representing inparticular H:

-   -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ and of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and

-   -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂, or

-   -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂, and

-   -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ and of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

or, when X′ represents BF₃M, W representing —OH or —NH₂,

-   -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

In the above and hereafter, in particular with respect to the aryls, theheterocycles, the heteroaryls, the alkenyls, the alkynyls, the alkyls,the rings optionally formed by R₁ and R₄, or R₁ and R₅, and the R^(a),R^(b) and R^(b′) groups, by substituted is meant the fact of beingsubstituted by:

-   -   one or more halogen atoms comprising fluorine, chlorine, bromine        or iodine,    -   hydroxy, amino or thio radicals optionally protected by “ad hoc”        protective groups,    -   —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR′, —OCOR^(a), —OCONHR^(a),        —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),        —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a),        —N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a),        —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b)        radicals, in which R^(a) and R^(b), identical or different,        represent the linear or branched cycloalkyl, cycloalkenyl,        aromatic, or aromatic or non-aromatic heterocyclic alkyl,        alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,        optionally substituted,    -   by alkyl radicals comprising 1 to 15 carbon atoms, optionally        substituted,    -   by linear or branched alkenyl radicals comprising 1 to 15 carbon        atoms, optionally substituted,    -   by linear or branched alkynyl radicals comprising 1 to 15 carbon        atoms, optionally substituted,    -   by linear or branched aryl radicals comprising 6 to 12 carbon        atoms, optionally substituted,    -   by aromatic or non-aromatic heterocycles comprising 2 to 12        carbon atoms, optionally substituted.

In the above and hereafter, the R^(a), R^(b) and R^(b′) groups,identical or different, represent linear or branched cycloalkyl,cycloalkenyl, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted.

The term “protective group of an alcohol function” represents a groupintended to protect an alcohol against undesirable reactions during thesynthesis steps. The protective groups of the alcohols which arecommonly used are described in Greene, “Protective Groups In OrganicSynthesis” (John Wiley & Sons, New York (1981). Examples of such groupsare the acetyl, benzoyl, benzyl pivaloyl, trityl, methoxytrityl,dimethoxytrityl, tetrahydropyranyl groups, and ethers such as themethyl, benzyl, allyl, ethoxyethyl, β-methoxyethoxymethyl,methoxymethyl, p-methoxybenzyl, methylthiomethyl, and silyl ethers.

The term “protective group of a thiol function” represents a groupintended to protect a thiol against undesirable reactions during thesynthesis steps.

The protective groups of the thiols commonly used are described inGreene, “Protective Groups In Organic Synthesis” (John Wiley & Sons, NewYork (1981). Examples of such groups are the benzoyl groups and etherssuch as the methyl, ethoxyethyl, benzyl, p-methoxybenzyl and silylethers.

The term “protective group of an amine function” represents a groupintended to protect an amine against undesirable reactions during thesynthesis steps. The protective groups of the amines commonly used aredescribed in Greene (ibid.). Examples of such groups are the carbamate,amide groups and the N-alkyl, acetal, N-benzyl, imine, enamine andN-heteroatom derivatives. In particular, the protective groups of theamines comprise the formyl, acetyl, benzoyl, pivaloyl, phenysulphonyl,p-toluenesulphonyl (tosyl), benzyl, t-butyloxycarbonyl (Boc),benzyloxycarbonyl (Cbz) and fluorenylmethyloxycarbonyl (Fmoc) groups.

As regards the conversion of the W₁ to the W group, the conversion of anester —COOR^(a) to the corresponding acid can be carried out by methodswell known to a person skilled in the art, for example bysaponification, or by acid hydrolysis.

The acid thus obtained can be converted to the corresponding aldehyde bypassing via a Weinreb amide of CONR—OR′ type then subsequent reductionby a hydride, for example DIBALH, in a solvent, for example THF, at lowtemperature.

The conversion of an ester to the corresponding aldehyde can for examplebe carried out by reduction of the ester by a hydride, in particularDIBA1H, in a solvent, for example THF, at low temperature, or byreduction to alcohol by the action of a hydride, in particular NaBH₄ orLiA1H₄, then subsequent oxidation to aldehyde by the action of anoxidizing reagent, for example a chromate reagent of PDC or PCC type, aperiodinane of the Dess-Martin reagent or IBX type, a sulphoxide in thepresence of a base according to the Swern reaction.

The conversion of a ketone —COR^(a) to the corresponding alcohol—CHR^(a)OH can for example be carried out by a reduction reaction understandard conditions known to a person skilled in the art, in particularthe action of a borohydride, preferentially NaBH₄, in an alcoholicsolvent, in particular methanol.

Said alcohol —CHR^(a)OH can be converted to —CHR^(a)OR^(b) by the actionof a strong base such as NaH or LDA then alkylation by an alkyl halideR^(b)—X.

The conversion of a ketone —COR^(a) to a corresponding alcohol—CR^(a)R^(b)OH can for example be carried out by the action of aGrignard reagent of R^(b)—MgX type in a THF or diethyl ether typesolvent. Said alcohol —CR^(a)R^(b)OH can be converted to—CR^(a)R^(b)OR^(b′) by an alkylation reaction as described previously.

The conversion of an amide —CONH₂, —CONHR^(a) or —CONR^(a)R^(b) to thecorresponding amine —CH₂NH₂, —CH₂NHR^(a) and —CH₂NR^(a)R^(b)respectively can for example be carried out by a reduction reaction ofthe amide function by the action of a hydride, preferentially LiA1H₄, ina solvent, in particular THF. If necessary, the protection of the amineby a protective group, for example the CBz group is carried outaccording to a procedure known to a person skilled in the art; when theprotective group is for example an amide, the action of an acid chlorideR^(a)COCl (for example EtCOCl) in the presence of a mineral or organicbase in a solvent, preferentially dimethylformamide, makes it possibleto form the corresponding amide.

The conversion of —CONH₂ to —CONHSO₂R^(a) is for example carried out bythe action of sulphonyl chloride ClSO₂R^(a) on the amide.

As regards the conversion of the W₂ to the W group, the deprotection ofZ′, Z and/or Z₂ is carried out according to procedures well known to aperson skilled in the art. For example the conversion of —NZZ₂ to —NHZcan be carried out by selective deprotection of the protective group Z₂,for example, in the case of Z=—COAlkyl and Z₂=Boc by acid hydrolysis(for example trifluoroacetic acid) in an organic solvent of thedichloromethane or dioxane type, or for example, in the case of Z=—Bnand Z₂=Fmoc by treatment with a secondary base (preferentiallypiperidine) in DMF, or for example, in the case of Z=COAlkyl and Z₂=CBzby hydrogenolysis in the presence of a catalyst (preferentially Pd/C) inan alcoholic solvent.

As regards the conversion of the —BF₃M to the X group, the conversion ofa —BF3M to a —B(OH)₂ group can for example be carried out by basichydrolysis in the presence of a mineral or organic base, for exampleNa₂CO₃ or LiOH, in a water/organic solvent mixture, for exampledichloromethane, acetonitrile or THF, or by acid hydrolysis in thepresence of a Lewis acid, for example FeCl₃, or preferentially bypassing to a dihalogenoborane by treatment with a silane, for exampleSiCl₄ or TMSC1, in a water/organic solvent mixture, for exampledichloromethane, acetonitrile, THF, dioxane or acetone at ambienttemperature then in situ hydrolysis.

The conversion of a —BF₃M to a B(OR)₂ group can for example be carriedout by intermediate passing via B(OH)₂ as described previously thensubsequent protection in boronic ester, for example B(Opinacol)₂, by theaction of the alcohol protective group (for example diol pinacol) in analcoholic solvent in the optional presence of an acid catalyst, forexample PTSA, and of a drying agent, for example MgSO₄ or a molecularsieve in a solvent, in particular an alcohol, toluene, or diethyl etherat ambient temperature or under reflux of the solvent or preferentiallyby passing to a dihalogenoborane by treatment with a silane, inparticular SiCl₄ or TMSC1, in a water/organic solvent mixture, forexample dichloromethane, acetonitrile, THF, dioxane or acetone, atambient temperature then treatment with the protective group in the formof diol, for example the diol pinacol, in an alcoholic solvent.

The conversion of a —BF₃M to a B(OR′)₃M group can for example be carriedout by intermediate passing via B(OH)₂ as described previously thentreatment with an alcohol R′OH in the presence of a strong mineral base,preferentially potash, in a solvent, preferentially warm toluene.

As regards the conversion of the —B(OR)₂ group to an X group, saidconversion step is in particular in the presence of MHF₂ when Xrepresents BF₃M, or is in particular a hydrolysis, more particularly inthe presence of a mineral, organic base or in the presence of a Lewisacid, when X represents B(OH)₂.

The conversion of a —B(OR)₂ to a B(OR′)₃M group can for example becarried out by treatment with an alcohol R′OH in the presence of astrong mineral base, preferentially potash, in a solvent, preferentiallywarm toluene.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional group chosen from —CHO,—COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, said processcomprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined previously, W₁ being chosen from the        group constituted by —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),        and —CONR^(a)R^(b), and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄, R₅ and M are as defined previously,    -   in the presence of a catalyst containing a transition metal, in        order to obtain a compound of the following formula:

-   -   in which R₁, R₂, R₄, R₅, W₁ and M are as defined previously,        if W is different from W₁ and/or X is different from MF₃B, said        process also comprising the following steps:    -   a step of conversion of W₁ to W making it possible to obtain

-   -   and    -   a step of conversion of —BF₃M to —X making it possible to obtain

-   -   or    -   a step of conversion of —BF₃M to —X making it possible to obtain

-   -   and    -   a step of conversion of W₁ to W making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional W₁ group chosen from —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), and —CONR^(a)R^(b), said processcomprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined previously, W₁ being as defined above,        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄, R₅ and M are as defined previously,    -   in the presence of a catalyst containing a transition metal, in        order to obtain a compound of the following formula:

-   -   in which R₁, R₂, R₄, R₅, W₁ and M are as defined above.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional group chosen from —CHO, —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, said processcomprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined previously, W₁ being chosen from the        group constituted by —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),        and —CONR^(a)R^(b), and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄, R₅ and M are as defined previously,    -   in the presence of a catalyst containing a transition metal, in        order to obtain a compound of the following formula:

-   -   in which R₁, R₂, R₄, R₅, W₁ and M are as defined previously,        said process also comprising the following step:    -   a step of conversion of W₁ to W making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional W₁ group chosen from —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), and —CONR^(a)R^(b), said processcomprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined previously, W₁ being as defined above,        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄, R₅ and M are as defined previously,    -   in the presence of a catalyst containing a transition metal, in        order to obtain a compound of the following formula:

-   -   in which R₁, R₂, R₄, R₅, W₁ and M are as defined above, said        process also comprising the following step:    -   a step of conversion of BF₃M to X, X representing B(OH)₂,        B(OR)₂, or B(OR′)₃M, making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional group chosen from —CHO, —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, said processcomprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined previously, W₁ being chosen from the        group constituted by —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),        and —CONR^(a)R^(b),        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄, R₅ and M are as defined previously,    -   in the presence of a catalyst containing a transition metal, in        order to obtain a compound of the following formula:

-   -   in which R₁, R₂, R₄, R₅, W₁ and M are as defined previously,        said process also comprising the following steps:    -   a step of conversion of W₁ to W making it possible to obtain

-   -   and    -   a step of conversion of BF₃M to X, X representing B(OH)₂,        B(OR)₂, or B(OR′)₃M, making it possible to obtain

-   -   or    -   a step of conversion of BF₃M to X, X representing B(OH)₂,        B(OR)₂, or B(OR′)₃M, making it possible to obtain

-   -   and    -   a step of conversion of W₁ to W making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a preparation process in which said catalyst containing a transitionmetal, said catalyst being in particular a palladium (II) complex, moreparticularly Pd(OAc)₂ or Pd(acac)₂, a copper (II) complex, moreparticularly CuSO₄, Cu(acac)₂, Cu(tBuSalen)₂, Cu(OTf)₂, a copper (I)complex, more particularly CuI or Cu(OTf), or a rhodium (II) complex,more particularly Rh₂(OAc)₄, Rh₂(Octanoate)₄ or Rh₂(5S-MEPY)₄ (Doylecatalyst).

According to an advantageous embodiment, the present invention relatesto a preparation process, in which W₁ represents —COOR^(a), R^(a) beingas defined previously.

According to an advantageous embodiment, the present invention relatesto a preparation process, in which R₂ is chosen from the groupconstituted by the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b), —CN and —NO₂ groups, in which R^(a) and R^(b), identicalor different, represent linear, cyclic or branched, aromatic, oraromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a preparation process, in which R₂ represents H.

According to an advantageous embodiment, the present invention relatesto a preparation process, in which R₁, R₄ and R₅ represent H, an aryl, aheterocycle, a heteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a preparation process, in which R₁, R₂, R₄ and R₅ represent H.

According to an advantageous embodiment, the present invention relatesto a preparation process, in which W represents a functional groupchosen from —CONH—SO₂-cyclopropyl, —CH₂—NH—CO—CH₂—CH₃, and the group ofthe following formula:

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to thefollowing formula (I-A)

in which:

X represents a substituted boron atom chosen from the group comprisingB(OH)₂, B(OR)₂, BF₃M, B(OR′)₃M in which:

-   -   R is an alkyl group comprising 1 to 14 carbon atoms or an aryl        group, optionally substituted, or is such that (OR)₂ forms a        ring between the two oxygen atoms, (OR)₂ being in particular        chosen from the group comprising the bivalent radicals deriving        from diols, such as O—CH₂—CH₂—O, O—CH₂—CH₂—CH₂—O,        O—CH₂—C(CH₃)₂—CH₂—O, O—C(CH₃)₂—CH₂—CH₂—C(CH₃)₂—O,        O—CH(CH₃)—CH₂—CH₂—CH(CH₃)—O, O—CH(Ph)-CH(Ph)-O,        O—CH(CH₃)—CH₂—C(CH₃)₂—O, O-o-Ph-O, O—CH₂—CH₂—NH—CH₂—CH₂—O,        O—CH₂—CH₂—N(CH₂—CH₂—CH₂—CH₃)—CH₂—CH₂—O, O—CH(COOH)—CH(COOH)—O        and its esters, and the bivalent radicals deriving from diacids,        such as OCO—CH₂—N(CH₃)—CH₂—COO,    -   R′ is an alkyl group comprising 1 to 14 carbon atoms or is such        that:        -   (OR′)₃ forms a ring between two of the oxygen atoms, (OR′)₃            then being in the form OR′(OR)₂, where R′ is an alkyl group            comprising 1 to 14 carbon atoms and (OR)₂ is as defined            above, or        -   (OR′)₃ forms a bicycle between the three oxygen atoms,            (OR′)₃ being in particular chosen from the group comprising            the trivalent radicals deriving from triols, such as            H₃C—C—(CH₂—O)₃,    -   M represents the lithium Li⁺ ion, the sodium Na⁺ ion, the        potassium K⁺ ion, the caesium Cs⁺ ion, the ammonium        R^(c)R^(d)R^(e)R^(f)N⁺ ion where R^(c), R^(d) R^(e), R^(f) are        chosen from H or a saturated carbon-containing chain comprising        in particular 1 to 6 carbon atoms chosen independently of one        another, and in particular X represents B(OH)₂, B(OR)₂ or BF₃K,

R₁ and R₄, identical or different, are chosen from the group constitutedby:

1. H

2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;at least one of the R₁ and R₄ groups representing H,

R₂ is chosen from the group constituted by the groups being able to berepresented by R₁ or R₄, as well as —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CONH—SO₂—R^(a), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, —CH₂—NH—COR^(a),

in which Z represents a protective group of an amine function, andin which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;said process comprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined above, W₁ being chosen from the group        constituted by —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), and        —CONR^(a)R^(b),        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄ and M are as defined above, in the presence of a        catalyst containing a transition metal, in order to obtain a        compound of the following formula:

-   -   in which R₁, R₂, R₄, W₁ and M are as defined above,        if W is different from W₁ and/or X is different from MF₃B, said        process also comprising the following steps:    -   a step of conversion of W₁ to W making it possible to obtain

-   -   in particular, when W₁=COOR^(a) and W=CHO, by reduction in order        to form the corresponding alcohol, then oxidation of said        alcohol, when W₁=—COOR^(a) and W=CH₂OH or —CH₂OR^(b), by the        formation of an aldehyde as described previously, then by        reduction of said aldehyde and optional alkylation, when        W₁=—COR^(a) and W=—CHR^(a)OH, —CHR^(a)OR^(b), by reduction then        optional alkylation of the alcohol obtained, when W₁=—COR^(a)        and W=CR^(a)R^(b)OH or —CR^(a)R^(b)OR^(b′) by addition of a        Grignard reagent then optional alkylation of the alcohol        obtained, when W₁=—CONH₂, —CONHR^(a) or —CONR^(a)R^(b) and        W=—CH₂NH₂, —CH₂NHR^(a), —CH₂NR^(a)R^(b), —CH₂NHZ or        —CH₂—NH—COR^(a), by reduction then optional protection by Z of        the amine obtained or optional reaction with the acid chloride        R^(a)COCl, when W₁=—CONH₂ and W=—CONHSO₂R^(a), by the action of        sulphonyl chloride ClSO₂R^(a) on the amide, and    -   a step of conversion of —BF₃M to —X making it possible to obtain

-   -   in particular, when X=B(OH)₂, by basic or acid hydrolysis, or by        passing via a dihalogenoborane, more particularly a        dichloroborane, when X=B(OR)₂, by passing via X=B(OH)₂ as        described previously then by the action of an alcohol, in        particular an alcohol of formula ROH, a diol or a triol, or by        passing via a dihalogenoborane, more particularly a        dichloroborane, then by the action of an alcohol, in particular        an alcohol of formula ROH, a diol or a triol,    -   or    -   a step of conversion of —BF₃M to —X making it possible to obtain

-   -   and    -   a step of conversion of W₁ to W making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to thefollowing formula (I-B)

in which:

-   -   M represents the lithium Li⁺ ion, the sodium Na⁺ ion, the        potassium K⁺ ion, the caesium Cs⁺ ion, the ammonium        R^(c)R^(d)R^(e)R^(f)N⁺ ion where R^(c), R^(d) R^(e), R^(f) are        chosen from H or a saturated carbon-containing chain comprising        in particular 1 to 6 carbon atoms chosen independently of one        another,

BF₃M representing in particular BF₃K,

-   -   R₁ and R₄, identical or different, are chosen from the group        constituted by:

1. H

2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;at least one of the R₁ and R₄ groups representing H,

R₂ is chosen from the group constituted by the groups being able to berepresented by R₁ or R₄, as well as —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted; R^(a) and R^(b)being able to be linked in order to form a ring, optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CONH—SO₂—R^(a), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, —CH₂—NH—COR^(a),

in which Z represents a protective group of an amine function, andin which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;said process comprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined above, W₁ being chosen from the group        constituted by —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), and        —CONRaRb,        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄ and M are as defined above,        -   in the presence of a catalyst containing a transition metal,            in order to obtain a compound of the following formula:

-   -   in which R₁, R₂, R₄, W₁ and M are as defined above,        if W is different from W₁, said process also comprising the        following steps:    -   a step of conversion of W₁ to W making it possible to obtain

-   -   in particular, when W₁=COOR^(a) and W=CHO, by reduction in order        to form the corresponding alcohol, then oxidation of said        alcohol, when W₁=—COOR^(a) and W=CH₂OH or —CH₂OR^(b), by the        formation of an aldehyde as described previously, then by        reduction of said aldehyde and optional alkylation, when        W₁=—COR^(a) and W=—CHR^(a)OH, —CHR^(a)OR^(b), by reduction then        optional alkylation of the alcohol obtained, when W₁=—COR^(a)        and W=CR^(a)R^(b)OH or —CR^(a)R^(b)OR^(b′) by addition of a        Grignard reagent then optional alkylation of the alcohol        obtained, when W₁=—CONH₂, —CONHR^(a) or —CONR^(a)R^(b) and        W=—CH₂NH₂, —CH₂NHR^(a), —CH₂NR^(a)R^(b), —CH₂NHZ or        —CH₂—NH—COR^(a), by reduction then optional protection by Z of        the amine obtained or optional reaction with the acid chloride        R^(a)COCl, when W₁=—CONH₂ and W=—CONHSO₂R^(a), by the action of        sulphonyl chloride ClSO₂R^(a) on the amide.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A), inwhich:

-   -   when R₁, R₂ and R₄ represent H and B represents B(OH)₂, B(OR)₂,        or B(OR′)₃M, then W is chosen from —COR^(a), —CONH₂, —CONHR^(a),        —CONR^(a)R^(b),    -   when R₁, R₂ and R₄ represent H and B represents BF₃M, then W is        chosen from —COOH, —COOR^(a), —CHO, —COR^(a)—CONH₂, —CONHR^(a),        —CONR^(a)R^(b),    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents        B(OH)₂, B(OR)₂, or B(OR′)₃M, then:        -   R₁ does not represent H, or        -   R₂ and R₄ do not represent H,    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents BF₃M,        then R₁ or R₂ do not represent H.    -   when W represents —COOH or —COOR^(a), and B represents B(OH)₂,        B(OR)₂, or B(OR′)₃M, then:        -   R₁ does not represent H, or        -   R₂ and R₄ do not represent H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-B), inwhich:

-   -   when R₁, R₂ and R₄ represent H, then W is chosen from —COOH,        —COOR^(a), —CHO, —COR^(a)—CONH₂, —CONHR^(a), —CONR^(a)R^(b),    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), then R₁ or R₂ do not        represent H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which said catalyst containing a transition metal is a palladium (II)complex, more particularly Pd(OAc)₂ or Pd(acac)₂, a copper (II) complex,more particularly CuSO₄, Cu(acac)₂, Cu(tBuSalen)₂, Cu(OTf)₂, a copper(I) complex, more particularly CuI or Cu(OTf), or a rhodium (II)complex, more particularly Rh₂(OAc)₄, Rh₂(Octanoate)₄ or Rh₂(5S-MEPY)₄(Doyle catalyst).

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which said catalyst containing a transition metal is a palladium (II)complex, more particularly Pd(OAc)₂ or Pd(acac)₂, or a copper (II)complex, more particularly CuSO₄, Cu(acac)₂, Cu(tBuSalen)₂, Cu(OTf)₂.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or(I-B), in which W₁ is chosen from the group constituted by —COOR^(a),—CONH₂, —CONHR^(a), and —CONR^(a)R^(b), R^(a) and R^(b) being as definedpreviously.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or(I-B), in which W₁ represents —COOR^(a), R^(a) being as definedpreviously, R^(a) representing in particular an alkyl, a cycloalkyl, abenzyl, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which W represents a functional group chosen

from —CHO, —COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b), —CONH—SO₂—R^(a), W₁ being in particular chosen from thegroup constituted by —COOR^(a), —CONH₂, —CONHR^(a), and —CONR^(a)R^(b),R^(a) and R^(b) being as defined previously, W₁ representing moreparticularly —COOR^(a), R^(a) being as defined previously, R^(a)representing in particular an alkyl, a cycloalkyl, a benzyl, optionallysubstituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which W represents a functional group chosen from —CHO, —COR^(a),—COOH and —COOR^(a), W₁ representing in particular —COOR^(a), R^(a)being as defined previously, R^(a) representing in particular an alkyl,a cycloalkyl, a benzyl, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which W and W₁ represent —COOR^(a), R^(a) being as definedpreviously, R^(a) representing in particular an alkyl, a cycloalkyl, abenzyl, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which W represents a functional group chosen from—CONH—SO₂-cyclopropyl, —CH₂—NH—CO—CH₂—CH₃ and the group of the followingformula:

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₂ represents H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₂ is chosen from the group constituted by the —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂ groups, inwhich R^(a) and R^(b), identical or different, represent linear, cyclicor branched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₂ is chosen from the group constituted by the —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups, in whichR^(a) and R^(b), identical or different, represent linear, cyclic orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₂ is chosen from the group constituted by the —COOR^(a),—CONH₂, —CONHR^(a) and —CONR^(a)R^(b) groups, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₁, R₂ and R₄ represent H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₁ represents H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₁ represents H and R₄ represents an aryl, a heterocycle, aheteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₄ represents H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₄ represents H and R₁ represents an aryl, a heterocycle, aheteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₁ and R₂ represent H and R₄ represents an aryl, a heterocycle,a heteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₂ and R₄ represent H and R₁ represents an aryl, a heterocycle,a heteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₁ represents H, R₄ represents an aryl, a heterocycle, aheteroaryl or an alkyl as defined previously, and R₂ is chosen from thegroup constituted by the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b) and —NO₂ groups,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₄ represents H, R₁ represents an aryl, a heterocycle, aheteroaryl or an alkyl as defined previously, and R₂ is chosen from thegroup constituted by the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b) and —NO₂ groups,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₁ and R₄ represent H, and R₂ is chosen from the groupconstituted by the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b) and —NO₂ groups,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₁ represents H, said catalyst being a palladium (II) complex,more particularly Pd(OAc)₂ or Pd(acac)₂.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-A) or (I-B)in which R₄ represents H, said catalyst being a copper (II) complex, inparticular CuSO₄, Cu(acac)₂, Cu(tBuSalen)₂, Cu(OTf)₂, or a copper (I)complex, in particular CuI or Cu(OTf), said catalyst being moreparticularly CuSO₄, Cu(acac)₂, Cu(tBuSalen)₂ or Cu(OTf)₂.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to thefollowing formula (I-C)

in which:

X represents a substituted boron atom chosen from the group comprisingB(OH)₂, B(OR)₂, BF₃M, B(OR′)₃M in which:

-   -   R is an alkyl group comprising 1 to 14 carbon atoms or an aryl        group, optionally substituted, or is such that (OR)₂ forms a        ring between the two oxygen atoms, (OR)₂ being in particular        chosen from the group comprising the bivalent radicals deriving        from diols, such as O—CH₂—CH₂—O, O—CH₂—CH₂—CH₂—O,        O—CH₂—C(CH₃)₂—CH₂—O, O—C(CH₃)₂—CH₂—CH₂—C(CH₃)₂—O,        O—CH(CH₃)—CH₂—CH₂—CH(CH₃)—O, O—CH(Ph)-CH(Ph)-O,        O—CH(CH₃)—CH₂—C(CH₃)₂—O, O-o-Ph-O, O—CH₂—CH₂—NH—CH₂—CH₂—O,        O—CH₂—CH₂—N(CH₂—CH₂—CH₂—CH₃)—CH₂—CH₂—O, O—CH(COOH)—CH(COOH)—O        and its esters, and the bivalent radicals deriving from diacids,        such as OCO—CH₂—N(CH₃)—CH₂—COO,    -   R′ is an alkyl group comprising 1 to 14 carbon atoms or is such        that:        -   (OR′)₃ forms a ring between two of the oxygen atoms, (OR′)₃            then being in the form OR′(OR)₂, where R′ is an alkyl group            comprising 1 to 14 carbon atoms and (OR)₂ is as defined            above, or        -   (OR′)₃ forms a bicycle between the three oxygen atoms,            (OR′)₃ being in particular chosen from the group comprising            the trivalent radicals deriving from triols, such as            H₃C—C—(CH₂—O)₃,    -   M represents the lithium Li⁺ ion, the sodium Na⁺ ion, the        potassium K⁺ ion, the caesium Cs⁺ ion, the ammonium        R^(c)R^(d)R^(e)R^(f)N⁺ ion where R^(c), R^(d) R^(e), R^(f) are        chosen from H or a saturated carbon-containing chain comprising        in particular 1 to 6 carbon atoms chosen independently of one        another,    -   and in particular X represents B(OH)₂, B(OR)₂ or BF₃K,

R₁ and R₄, identical or different, are chosen from the group constitutedby:

1. H

2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;at least one of the R₁ and R₄ groups representing H,

R₂ is chosen from the group constituted by H and the —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b),

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;said process comprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined above, W₁ being chosen from the group        constituted by —COOR^(a), —CONH₂, —CONHR^(a), and        —CONR^(a)R^(b),        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄ and M are as defined above,        -   in the presence of a catalyst containing a transition metal,            said catalyst being a palladium (II) complex, more            particularly Pd(OAc)₂ or Pd(acac)₂, or a copper (II)            complex, more particularly CuSO₄, Cu(acac)₂, Cu(tBuSalen)₂,            Cu(OTf)₂, said catalyst being in particular a palladium (II)            complex, more particularly        -   Pd(OAc)₂ or Pd(acac)₂, when R₁ represents H, said catalyst            being in particular a copper (II) complex, in particular            CuSO₄,        -   Cu(acac)₂, Cu(tBuSalen)₂, Cu(OTf)₂, when R₄ represents H, in            order to obtain a compound of the following formula:

-   -   in which R₁, R₂, R₄, W₁ and M are as defined above,        if W is different from W₁ and/or X is different from MF₃B, said        process also comprising the following steps:    -   a step of conversion of W₁ to W making it possible to obtain

-   -   in particular, when W₁=COOR^(a) and W=CHO, by reduction in order        to form the corresponding alcohol, then oxidation of said        alcohol, when W₁=—CONH₂ and W=—CONHSO₂R^(a), by the action of        sulphonyl chloride ClSO₂R^(a) on the amide,    -   and    -   a step of conversion of —BF₃M to —X making it possible to obtain

-   -   in particular, when X=B(OH)₂, by basic or acid hydrolysis, or by        passing via a dihalogenoborane, more particularly a        dichloroborane, when X=B(OR)₂, by passing via X=B(OH)₂ as        described previously then by the action of an alcohol, in        particular an alcohol of formula ROH, a diol or a triol, or by        passing via a dihalogenoborane, more particularly a        dichloroborane, then by the action of an alcohol, in particular        an alcohol of formula ROH, a diol or a triol,    -   or    -   a step of conversion of —BF₃M to —X making it possible to obtain

-   -   and    -   a step of conversion of W₁ to W making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to thefollowing formula (I-D)

in which:

M represents the lithium Li⁺ ion, the sodium Na⁺ ion, the potassium K⁺ion, the caesium Cs⁺ ion, the ammonium R^(c)R^(d)R^(e)R^(f)N⁺ ion whereR^(c), R^(d) R^(e), R^(f) are chosen from H or a saturatedcarbon-containing chain comprising in particular 1 to 6 carbon atomschosen independently of one another,

BF₃M representing in particular BF₃K,

R₁ and R₄, identical or different, are chosen from the group constitutedby:

1. H

2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;at least one of the R₁ and R₄ groups representing H,

R₂ is chosen from the group constituted by H and the —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups, in whichR^(a) and R^(b), identical or different, represent linear, cyclic orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

said process comprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined above, W₁ being chosen from the group        constituted by —COOR^(a), —CONH₂, —CONHR^(a), and        —CONR^(a)R^(b),        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄ and M are as defined above,        -   in the presence of a catalyst containing a transition metal,            said catalyst being a palladium (II) complex, more            particularly Pd(OAc)₂ or Pd(acac)₂, or a copper (II)            complex, more particularly CuSO₄, Cu(acac)₂, Cu(tBuSalen)₂,            Cu(OTf)₂, said catalyst being in particular a palladium (II)            complex, more particularly Pd(OAc)₂ or Pd(acac)₂, when R₁            represents H,        -   said catalyst being in particular a copper (II) complex, in            particular CuSO₄, Cu(acac)₂, Cu(tBuSalen)₂, Cu(OTf)₂, when            R₄ represents H,        -   in order to obtain a compound of the following formula:

-   -   in which R₁, R₂, R₄, W₁ and M are as defined above,        if W is different from W₁, said process also comprising the        following steps:    -   a step of conversion of W₁ to W making it possible to obtain

-   -   in particular, when W₁=COOR^(a) and W=CHO, by reduction in order        to form the corresponding alcohol, then oxidation of said        alcohol, when W₁=—CONH₂ and W=—CONHSO₂R^(a), by the action of        sulphonyl chloride ClSO₂R^(a) on the amide.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C), inwhich:

-   when R₁, R₂ and R₄ represent H and B represents B(OH)₂, B(OR)₂, or    B(OR′)₃M, then W is chosen from —COR^(a), —CONH₂, —CONHR^(a),    —CONR^(a)R^(b),-   when W represents —COOH or —COOR^(a), and B represents B(OH)₂,    B(OR)₂, or B(OR′)₃M,    -   then:        -   R₁ does not represent H, or        -   R₂ and R₄ do not represent H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or(I-D), in which W₁ represents —COOR^(a), R^(a) being as definedpreviously, R^(a) representing in particular an alkyl, a cycloalkyl, abenzyl, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which W represents a functional group chosen from —CHO, —COR^(a),—COOH and —COOR^(a), W₁ representing in particular —COOR^(a), R^(a)being as defined previously, R^(a) representing in particular an alkyl,a cycloalkyl, a benzyl, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which W and W₁ represent —COOR^(a), R^(a) being as definedpreviously, R^(a) representing in particular an alkyl, a cycloalkyl, abenzyl, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₂ represents H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₂ is chosen from the group constituted by the —COOR^(a),—CONH₂, —CONHR^(a) and —CONR^(a)R^(b) groups, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₁, R₂ and R₄ represent H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₁ represents H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₁ represents H and R₄ represents an aryl, a heterocycle, aheteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₄ represents H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₄ represents H and R₁ represents an aryl, a heterocycle, aheteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₁ and R₂ represent H and R₄ represents an aryl, a heterocycle,a heteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₂ and R₄ represent H and R₁ represents an aryl, a heterocycle,a heteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₁ represents H, R₄ represents an aryl, a heterocycle, aheteroaryl or an alkyl as defined previously, and R₂ is chosen from thegroup constituted by the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b) and —NO₂ groups,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₄ represents H, R₁ represents an aryl, a heterocycle, aheteroaryl or an alkyl as defined previously, and R₂ is chosen from thegroup constituted by the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b) and —NO₂ groups,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₁ and R₄ represent H, and R₂ is chosen from the groupconstituted by the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b) and —NO₂ groups,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a preparation process, in which W represents —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH, —CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ,—CHR^(a)NHZ, said process comprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R^(a) is as defined previously,        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which M is as defined previously, M representing in        particular K, in the presence of a catalyst containing a        transition metal, in order to obtain a compound of the following        formula:

-   -   in which R^(a) and M are as defined above,        if W is different from —COOR^(a) and/or X is different from        MF₃B, said process also comprising the following steps:    -   a step of conversion of —COOR^(a) to W making it possible to        obtain

-   -   and    -   a step of conversion of —BF₃M to —X making it possible to obtain

-   -   or    -   a step of conversion of —BF₃M to —X making it possible to obtain

-   -   and    -   a step of conversion of —COOR^(a) to W making it possible to        obtain

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I), in theform of a trans racemic compound of formula (I-1):

and its enantiomer, (I-1) in which X, R₁, R₂, R₄, R₅ and W are asdefined previously, said process comprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined above, W₁ being chosen from the group        constituted by —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), and        —CONR^(a)R^(b), and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄, R₅ and M are as defined above,        -   in the presence of a catalyst containing a transition metal,            in order to obtain a compound of the following formula:

-   -   in which R₁, R₂, R₄, R₅, W₁ and M are as defined above, in the        form of a mixture comprising the pairs of enantiomers of the        following formulae:

and its enantiomer, and

and its enantiomer,

-   -   a step of separation of said pairs of enantiomers, in particular        by recrystallization, in order to obtain the following pair of        trans enantiomers:

and its enantiomer,if W is different from W₁ and/or X is different from MF₃B, said processalso comprising the following steps:

-   -   a step of conversion of W₁ to W making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of —BF₃M to —X making it possible to obtain

and its enantiomer from

and its enantiomer

-   -   or    -   a step of conversion of —BF₃M to —X making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of W₁ to W making it possible to obtain

and its enantiomer from

and its enantiomer.

The term “trans” relates to the X group and the W group, and signifiesthat said X and W groups are not in the same half space, with respect tothe plane defined by the cyclopropyl.

For example the compound potassium

[(1S,2S)-2-ethoxycarbonylcyclopropyl]-trifluoroborate of the followingformula:

is trans.

The term “trans” relates to a pair of enantiomers. The following twocompounds:

are trans.

Thus, when a “trans” compound of the following formula is mentioned:

it refers to the following pair of enantiomers:

When R₂=W, for example R₂=W=—COOR^(a), the concept of “trans” cannot bedefined, and the following pair of enantiomers is considered:

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I), in whichR₁, R₂, R₄ and R₅ represent H, in the form of a racemic trans compoundof formula (I-1a):

and its enantiomer, (I-1a)in which X and W are as defined previously, said process comprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   W₁ being chosen from the group constituted by —COR^(a),        —COOR^(a), —CONH₂, —CONHR^(a), and —CONR^(a)R^(b), W₁        representing in particular —COOR^(a),        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which M is as defined above,    -   in the presence of a catalyst containing a transition metal, in        order to obtain a compound of the following formula:

-   -   in which W₁ and M are as defined above, in the form of a mixture        comprising the pairs of enantiomers of the following formulae:

and its enantiomer, and

and its enantiomer,

-   -   a step of separation of said pairs of enantiomers, in particular        by recrystallization, in order to obtain the following pair of        trans enantiomers:

and its enantiomer,if W is different from W₁ and/or X is different from MF₃B, said processalso comprising the following steps:

-   -   a step of conversion of W₁ to W making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of —BF₃M to —X making it possible to obtain

and its enantiomer from

and its enantiomer

-   -   or    -   a step of conversion of —BF₃M to —X making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of W₁ to W making it possible to obtain

and its enantiomer from

and its enantiomer.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I), in theform of a racemic cis compound of formula (I-2):

and its enantiomer, (I-2)in which X, R₁, R₂, R₄, R₅ and W are as defined previously, said processcomprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   in which R₂ is as defined above, W₁ being chosen from the group        constituted by —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), and        —CONR^(a)R^(b),        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which R₁, R₄, R₅ and M are as defined above,        -   in the presence of a catalyst containing a transition metal,            in order to obtain a compound of the following formula:

in which R₁, R₂, R₄, R₅, W₁ and M are as defined above, in the form of amixture comprising the pairs of enantiomers of the following formulae:

and its enantiomer, and

and its enantiomer,

-   -   a step of separation of said pairs of enantiomers, in particular        by recrystallization, in order to obtain the following pair of        trans enantiomers:

and its enantiomer,if W is different from W₁ and/or X is different from MF₃B, said processalso comprising the following steps:

-   -   a step of conversion of W₁ to W making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of —BF₃M to —X making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   or    -   a step of conversion of —BF₃M to —X making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of W₁ to W making it possible to obtain

and its enantiomer from

and its enantiomer.

The term “cis” relates to both the X group and the W group, andsignifies that said groups X and W are in the same half space, withrespect to the plane defined by the cyclopropyl.

For example the compound potassium

[(1S,2R)-2-ethoxycarbonylcyclopropyl]-trifluoroborate of the followingformula:

is cis.

The term “cis” relates to a pair of enantiomers. The following twocompounds:

are cis.

Thus, when a “cis” compound of the following formula is mentioned:

it refers to the following pair of enantiomers:

When R₂=W, for example R₂=W=—COOR^(a), the concept of “cis” cannot bedefined, and the following pair of enantiomers is considered:

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I), in whichR₁, R₂, R₄ and R₅ represent H, in the form of a racemic cis compound offormula (I-2a):

and its enantiomer, (I-2a)in which X and W are as defined previously, said process comprising:

-   -   a step of reaction between:        -   a diazoic derivative of the following formula:

-   -   W₁ being chosen from the group constituted by —COR^(a),        —COOR^(a), —CONH₂, —CONHR^(a), and —CONR^(a)R^(b), W₁        representing in particular —COOR^(a),        -   and        -   a vinyltrifluoroborate compound of the following formula:

-   -   in which M is as defined above,    -   in the presence of a catalyst containing a transition metal, in        order to obtain a compound of the following formula:

-   -   in which W₁ and M are as defined above, in the form of a mixture        comprising the pairs of enantiomers of the following formulae:

and its enantiomer, and

and its enantiomer,

-   -   a step of separation of said pairs of enantiomers, in particular        by recrystallization, in order to obtain the following pair of        cis enantiomers:

and its enantiomer,if W is different from W₁ and/or X is different from MF₃B, said processalso comprising the following steps:

-   -   a step of conversion of W₁ to W making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of —BF₃M to —X making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   or    -   a step of conversion of —BF₃M to —X making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of W₁ to W making it possible to obtain

and its enantiomer from

and its enantiomer.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional group chosen from —OH, —OR^(a),—OZ′, —NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂, in particular from—OH, —OR^(a) and —OZ′, said process comprising:

-   -   the treatment of a compound of the following formula:

-   -   in which R₂ is as defined previously, R₂ representing in        particular H,    -   and in which W₂ represents a functional group chosen from        —OR^(a), —OZ′, —NR^(a)R^(b) and —NZZ₂, in particular from        —OR^(a) and —OZ′, Y being a halide, in particular —Br, Y′ being        a halide, in particular —Br, or H,    -   by:        -   a strong base, in particular an alkyl lithium, more            particularly n-butyllithium or sec-butyllithium, then        -   a compound of formula X″—B(OR)₂, R being as defined above,            X″ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

-   -   in which R, R₂ and W₂ are as defined above,    -   or    -   a reaction of the Simmons-Smith type starting from a compound of        the following formula:

-   -   in which R₁ and R₂ are as defined previously, R₁ and R₂        representing in particular H, W₂ representing a functional group        chosen from —OR^(a), —OZ′, —NR^(a)R^(b) and —NZZ₂, in particular        from —OR^(a) and —OZ′, X′ representing B(OR)₂ or BF₃M, in        particular B(OR)₂, in which R and M are as defined previously,    -   in order to obtain a compound of the following formula:

-   -   in which R₁, R₂, X′ and W₂ are as defined above,        if W represents —OH or —NH₂, and/or X is different from B(OR)₂,        said process also comprising the following steps, R₁        representing in particular H:    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

-   -   and    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂,

-   -   or    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂,

-   -   and    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

-   -   or, when X′ represents BF₃M, W representing —OH or —NH₂,    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional W₂ group chosen from —OR^(a),—OZ′, —NR^(a)R^(b) and —NZZ₂, in particular from —OR′ and —OZ′, saidprocess comprising:

-   -   the treatment of a compound of the following formula:

-   -   in which R₂ is as defined previously,    -   and in which W₂ is as described above, Y being a halide, in        particular —Br, Y′ being a halide, in particular —Br, or H, by:        -   a strong base, in particular butyllithium, more particularly            n-butyllithium, then        -   a compound of formula X″—B(OR)₂, R being as defined above,            X″ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

-   -   in which R and W₂ are as defined above,    -   or    -   a reaction of the Simmons-Smith type starting from a compound of        the following formula:

-   -   in which W₂, R₁ and R₂ are as defined previously, X′        representing B(OR)₂ or BF₃M, in particular B(OR)₂, in which R        and M are as defined previously,    -   in order to obtain a compound of the following formula:

-   -   in which R₁, R₂, X′ and W₂ are as defined above.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents an —OH or —NH₂ functional group, inparticular —OH:

-   -   the treatment of a compound of the following formula:

-   -   in which R₂ is as defined previously,    -   and in which W₂ represents a functional group chosen from        —OR^(a), —OZ′ and —NZZ₂, in particular from —OR^(a) and —OZ′, W₂        representing in particular —OZ′, Y being a halide, in particular        —Br, Y′ being a halide, in particular —Br, or H, by:        -   a strong base, in particular an alkyl lithium, more            particularly n-butyllithium or sec-butyllithium, then        -   a compound of formula X″—B(OR)₂, R being as defined above,            X″ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

in which R and W₂ are as defined above,

-   -   or    -   a reaction of the Simmons-Smith type starting from a compound of        the following formula:

-   -   in which R₁ and R₂ are as defined previously, W₂ representing a        functional group chosen from —OR^(a), —OZ′ and —NZZ₂, in        particular from —OR^(a) and —OZ′, W₂ representing in particular        —OZ′, X′ representing B(OR)₂ or BF₃M, in particular B(OR)₂, in        which R and M are as defined previously,    -   in order to obtain a compound of the following formula:

-   -   in which R₁, R₂, X′ and W₂ are as defined above,        said process also comprising the following step, R₁ representing        in particular H:    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

-   -   or, when X′ represents BF₃M,    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional W₂ group chosen from —OR^(a),—OZ′, —NR^(a)R^(b) and —NZZ₂, in particular from —OR^(a) and —OZ′, saidprocess comprising:

-   -   the treatment of a compound of the following formula:

-   -   in which R₂ is as defined previously,    -   and in which W₂ is as described above, Y being a halide, in        particular —Br, Y′ being a halide, in particular —Br, or H, by:        -   a strong base, in particular an alkyl lithium, more            particularly n-butyllithium or sec-butyllithium then        -   a compound of formula X″—B(OR)₂, R being as defined above,            X″ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

-   -   in which R and W₂ are as defined above,    -   or    -   a reaction of the Simmons-Smith type starting from a compound of        the following formula:

-   -   in which W₂, R₁ and R₂ are as defined previously, X′        representing B(OR)₂ or BF₃M, in particular B(OR)₂, in which R        and M are as defined previously,    -   in order to obtain a compound of the following formula:

-   -   in which R₁, R₂, X′ and W₂ are as defined above,        said process also comprising the following step, R₁ representing        in particular H:    -   a step of conversion of B(OR)₂ to X, X representing B(OH)₂, BF₃M        or B(OR′)₃M, making it possible to obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a —OH or —NH₂ functional group, in particular—OH, said process comprising:

-   -   the treatment of a compound of the following formula:

in which R₂ is as defined previously,

-   -   and in which W₂ represents a functional group chosen from        —OR^(a), —OZ′ and —NZZ₂, in particular from —OR^(a) and —OZ′, W₂        representing in particular —OZ′, Y being a halide, in particular        —Br, Y′ being a halide, in particular —Br, or H, by:        -   a strong base, in particular butyllithium, more particularly            n-butyllithium, then        -   a compound of formula X″—B(OR)₂, R being as defined above,            X″ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

-   -   in which R and W₂ are as defined above,    -   or    -   a reaction of the Simmons-Smith type starting from a compound of        the following formula:

-   -   in which R₁ and R₂ are as defined previously, W₂ representing a        functional group chosen from —OR^(a), —OZ′ and —NZZ₂, in        particular from —OR^(a) and —OZ′, W₂ representing in particular        —OZ′, X′ representing B(OR)₂ or BF₃M, in particular B(OR)₂, in        which R and M are as defined previously,    -   in order to obtain a compound of the following formula:

-   -   in which R₁, R₂, X′ and W₂ are as defined above,        said process also comprising the following steps, R₁        representing in particular H:    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

-   -   and    -   a step of conversion of B(OR)₂ to X, X representing B(OH)₂, BF₃M        or B(OR′)₃M, making it possible to obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂,

-   -   or    -   a step of conversion of B(OR)₂ to X, X representing B(OH)₂, BF₃M        or B(OR′)₃M, making it possible to obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂,

-   -   and    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

-   -   or, when X′ represents BF₃M, W representing —OH or —NH₂,    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional group chosen from —OH, —OR^(a),—OZ′, —NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂, in particular from—OH, —OR^(a) and —OZ′, said process comprising:

-   -   the treatment of a compound of the following formula:

-   -   in which R₂ is as defined previously,    -   and in which W₂ represents a functional group chosen from        —OR^(a), —OZ′, —NR^(a)R^(b) and —NZZ₂, in particular from        —OR^(a) and —OZ′, Y being a halide, in particular —Br, Y′ being        a halide, in particular —Br, or H, by:        -   a strong base, in particular an alkyl lithium, more            particularly n-butyllithium or sec-butyllithium then        -   a compound of formula X″—B(OR)₂, R being as defined above,            X″ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

in which R, R₂ and W₂ are as defined above, if W represents —OH or —NH₂,and/or X is different from B(OR)₂, said process also comprising thefollowing steps:

-   -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W2 represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

-   -   and    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂,

-   -   or    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂,

-   -   and    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a preparation process, in which R₂ represents H.

According to an advantageous embodiment, the present invention relatesto a preparation process, in which R₂ represents a linear, cyclic orbranched alkyl group comprising 1 to 15 carbon atoms, optionallysubstituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional group chosen from —OH, —OR^(a),—OZ′, —NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂, in particular from—OH, —OR^(a) and —OZ′, said process comprising:

-   -   a reaction of the Simmons-Smith type starting from a compound of        the following formula:

-   -   in which R₁ and R₂ are as defined previously, W₂ representing a        functional group chosen from —OR^(a), —OZ′, —NR^(a)R^(b) and        —NZZ₂, in particular from —OR^(a) and —OZ′, X′ representing        B(OR)₂ or BF₃M, in particular B(OR)₂, in which R and M are as        defined previously,    -   in order to obtain a compound of the following formula:

-   -   in which R₁, R₂, X′ and W₂ are as defined above,        if W represents —OH or —NH₂, and/or X is different from B(OR)₂,        said process also comprising the following steps:    -   when X′ represents B(OR)₂,    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

-   -   and    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂, or

-   -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

said conversion step being in particular in the presence of MHF₂ when Xrepresents BF₃M, or in particular a hydrolysis, more particularly in thepresence of a mineral, organic base or in the presence of a Lewis acid,when X represents B(OH)₂, and

-   -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W2 represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

-   -   or, when X′ represents BF₃M, W representing —OH or —NH₂,    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

According to an advantageous embodiment, the present invention relatesto a preparation process, in which R₁ and R₂ represent H.

According to an advantageous embodiment, the present invention relatesto a preparation process, in which R₁ and R₂ represent, independently ofone another, H or a linear, cyclic or branched alkyl group comprising 1to 15 carbon atoms, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional group chosen from —OH, —OR^(a),—OZ′, —NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂, in particular from—OH, —OR^(a) and —OZ′,

in the form of a racemic trans compound of formula (I-1c):

and its enantiomer, (I-1c) in which X and W are as defined previously,said process comprising:

-   -   the treatment of a compound of the following formula:

-   -   in which R₂ is as defined previously, and in which W₂ represents        a functional group chosen from —OR^(a), —OZ′, —NR^(a)R^(b) and        —NZZ₂, in particular from —OR^(a) and —OZ′, Y being a halide, in        particular —Br, Y′ being a halide, in particular —Br, by:        -   a strong base, in particular an alkyl lithium, more            particularly n-butyllithium or sec-butyllithium then        -   a compound of formula X″—B(OR)₂, R being as defined above,            X″ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

and its enantiomer,

-   -   in which R and W are as defined above,        or the following steps:    -   the treatment of a compound of the following formula:

-   -   in which R₂ is as defined previously,    -   and in which W₂ represents a functional group chosen from        —OR^(a), —OZ′, —NR^(a)R^(b) and —NHZ, in particular from —OR^(a)        and —OZ′, Y being a halide, in particular —Br, Y′ being a        halide, in particular —Br,    -   by a strong base, in particular butyllithium, more particularly        n-butyllithium, in order to obtain a compound of the following        formula:

and its enantiomer,

-   -   in which W is as defined above,    -   the treatment of the compound of the following formula:

and its enantiomer,

-   -   in which W is as defined above,    -   by:        -   a strong base, in particular an alkyl lithium, more            particularly n-butyllithium or sec-butyllithium, then

a compound of formula X″—B(OR)₂, R being as defined above, X″representing H, an O-alkyl group comprising 1 to 14 carbon atoms or anO-aryl group, optionally substituted,

-   -   in order to obtain a compound of the following formula:

and its enantiomer,

-   -   in which R and W are as defined above,        or the following step:    -   a reaction of the Simmons-Smith type starting from a compound of        the following formula:

-   -   in which R₁ and R₂ are as defined previously, W₂ representing a        functional group chosen from —OR^(a), —OZ′, —NR^(a)R^(b) and        —NZZ₂, in particular from —OR^(a) and —OZ′, X′ representing        B(OR)₂ or BF₃M, in particular B(OR)₂, in which R and M are as        defined previously,    -   in order to obtain a compound of the following formula:

and its enantiomer,

-   -   in which R₁, R₂, X′ and W₂ are as defined above,        if W represents —OH or —NH₂, and/or X is different from B(OR)₂,        said process also comprising the following steps, R₁        representing in particular H:    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

and its enantiomer from

and its enantiomer, said conversion step being in particular in thepresence of MHF₂ when X represents BF₃M, or in particular a hydrolysis,more particularly in the presence of a mineral, organic base or in thepresence of a Lewis acid, when X represents B(OH)₂,

-   -   or    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

and its enantiomer from

and its enantiomer,

-   -   said conversion step being in particular in the presence of MHF₂        when X represents BF₃M, or in particular a hydrolysis, more        particularly in the presence of a mineral, organic base or in        the presence of a Lewis acid, when X represents B(OH)₂, and    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   or, when X′ represents BF₃M, W representing —OH or —NH₂,    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional group chosen from —OH, —OR^(a),—OZ′, —NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂, in particular from—OH, —OR^(a) and —OZ′,

in the form of a racemic trans compound of formula (I-1b):

and its enantiomer, (I-1b)in which X and W are as defined previously, said process comprising:

-   -   the treatment of a compound of the following formula:

-   -   in which R₂ is as defined previously,    -   and in which W₂ represents a functional group chosen from        —OR^(a), —OZ′, —NR^(a)R^(b) and —NZZ₂, in particular from        —OR^(a) and —OZ′, Y being a halide, in particular —Br, Y′ being        a halide, in particular —Br,    -   by:        -   a strong base, in particular an alkyl lithium, more            particularly n-butyllithium or sec-butyllithium, then        -   a compound of formula X″—B(OR)₂, R being as defined above,            X″ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

and its enantiomer,

-   -   in which R and W are as defined above,        or the following steps:    -   the treatment of a compound of the following formula:

-   -   in which R₂ is as defined previously,    -   and in which W₂ represents a functional group chosen from        —OR^(a), —OZ′, —NR^(a)R^(b) and —NZZ₂, in particular from        —OR^(a) and —OZ′, Y being a halide, in particular —Br, Y′ being        a halide, in particular —Br,    -   by a strong base, in particular an alkyl lithium, more        particularly n-butyllithium or sec-butyllithium, in order to        obtain a compound of the following formula:

and its enantiomer,

-   -   in which W is as defined above,    -   the treatment of the compound of the following formula:

and its enantiomer,

-   -   in which W is as defined above,    -   by:        -   a strong base, in particular an alkyl lithium, more            particularly n-butyllithium or sec-butyllithium, then        -   a compound of formula X″—B(OR)₂, R being as defined above,            X″ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

and its enantiomer,

-   -   in which R and W are as defined above,        if W represents —OH or —NH₂, and/or X is different from B(OR)₂,        said process also comprising the following steps:    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

and its enantiomer from

and its enantiomer, said conversion step being in particular in thepresence of MHF₂ when X represents BF₃M, or in particular a hydrolysis,more particularly in the presence of a mineral, organic base or in thepresence of a Lewis acid, when X represents B(OH)₂, or

-   -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

and its enantiomer from

and its enantiomer,

-   -   said conversion step being in particular in the presence of MHF₂        when X represents BF₃M, or in particular a hydrolysis, more        particularly in the presence of a mineral, organic base or in        the presence of a Lewis acid, when X represents B(OH)₂, and    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   or, when X′ represents BF₃M, W representing —OH or —NH₂,    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W2 represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional group chosen from —OH, —OR^(a),—OZ′, —NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂, in particular from—OH, —OR^(a) and —OZ′, in the form of a racemic trans compound offormula (I-1c):

and its enantiomer, (I-1c)in which X and W are as defined previously, said process comprising:

-   -   a step of reaction between a compound of the following formula:

-   -   R₂ being as defined previously, W₂ representing a functional        group chosen from —OR^(a), —OZ′, —NR^(a)R^(b) and —NZZ₂, in        particular from —OR^(a) and —OZ′,    -   and a compound of the following formula:

-   -   R₁ being as defined previously, X′ representing B(OR)₂ or BF₃M,        in particular B(OR)₂, in the presence of a catalyst comprising a        transition metal chosen from the group constituted by nickel,        molybdenum, tungsten, ruthenium, in particular molybdenum or        ruthenium, said catalyst being more particularly a Shrock        catalyst, a 1^(st) generation Grubbs catalyst, a 2^(nd)        generation Grubbs catalyst, or a catalyst of the following        formula:

-   -   in order to form a compound of the following formula:

-   -   in which R₁, R₂, X′ and W₂ are as defined above,    -   a reaction of the Simmons-Smith type starting from a compound of        the following formula:

-   -   in which R₁, R₂, X′ and W₂ are as defined above, in order to        obtain a compound of the following formula:

and its enantiomer, in which R₁, R₂, X′ and W₂ are as defined above,

if W represents —OH or —NH₂, and/or X is different from B(OR)₂, saidprocess also comprising the following steps:

-   -   when X′ represents B(OR)₂,    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

and its enantiomer from

and its enantiomer,

-   -   said conversion step being in particular in the presence of MHF₂        when X represents BF₃M, or in particular a hydrolysis, more        particularly in the presence of a mineral, organic base or in        the presence of a Lewis acid, when X represents B(OH)₂, or    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

and its enantiomer from

and its enantiomer,

-   -   said conversion step being in particular in the presence of MHF₂        when X represents BF₃M, or in particular a hydrolysis, more        particularly in the presence of a mineral, organic base or in        the presence of a Lewis acid, when X represents B(OH)₂,    -   and    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W2 represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   or, when X′ represents BF₃M, W representing —OH or —NH₂,    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound corresponding to formula(I), in which W represents a functional group chosen from —OH, —OR^(a),—OZ′, —NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂, in particular from—OH, —OR^(a) and —OZ′, in the form of a racemic cis compound of formula(I-2b):

and its enantiomer, (I-2b)in which X and W are as defined previously, said process comprising:

-   -   a reaction of the Simmons-Smith type starting from a compound of        the following formula:

in which Y is as defined previously, W₂ representing a functional groupchosen from —OR^(a), —OZ′, —NR^(a)R^(b) and —NZZ₂, in particular from—OR^(a) and —OZ′, in order to obtain a compound of the followingformula:

and its enantiomer,

-   -   in which Y and W₂ are as defined above, and    -   the treatment of a compound of the following formula:

and its enantiomer,

-   -   in which Y and W₂ are as defined above,    -   by:        -   a strong base, in particular an alkyl lithium, more            particularly n-butyllithium or sec-butyllithium, then        -   a compound of formula X″—B(OR)₂, R being as defined above,            X″ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

and its enantiomer,

-   -   in which R and W are as defined above,    -   or    -   the treatment of a compound of the following formula:

-   -   in which Y and W₂ are as defined above,    -   by:        -   a strong base, in particular an alkyl lithium, more            particularly n-butyllithium or sec-butyllithium, then        -   a compound of formula X′—B(OR)₂, R being as defined above,            X′ representing H, an O-alkyl group comprising 1 to 14            carbon atoms or an O-aryl group, optionally substituted,    -   in order to obtain a compound of the following formula:

-   -   in which R and W₂ are as defined above, and    -   a reaction of the Simmons-Smith type starting from a compound of        the following formula:

-   -   in which Y is as defined previously, W₂ representing a        functional group chosen from —OR^(a), —OZ′, —NR^(a)R^(b) and        —NZZ₂, in order to obtain a compound of the following formula:

and its enantiomer,

-   -   in which R and W₂ are as defined above;        if W represents —OH or —NH₂, and/or X is different from B(OR)₂,        said process also comprising the following steps:    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer,

-   -   and    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

and its enantiomer from

and its enantiomer,

-   -   said conversion step being in particular in the presence of MHF₂        when X represents BF₃M, or in particular a hydrolysis, more        particularly in the presence of a mineral, organic base or in        the presence of a Lewis acid, when X represents B(OH)₂,    -   or    -   a step of conversion of B(OR)₂ to —X making it possible to        obtain

and its enantiomer from

and its enantiomer,

-   -   said conversion step being in particular in the presence of MHF₂        when X represents BF₃M, or in particular a hydrolysis, more        particularly in the presence of a mineral, organic base or in        the presence of a Lewis acid, when X represents B(OH)₂, and    -   a step of conversion of W₂ to W, in particular the deprotection        of the Z′ group when W₂ represents —OZ′ or of the Z and Z₂        groups when W₂ represents —NZZ₂, making it possible to obtain

and its enantiomer from

and its enantiomer.

The invention also relates to a compound corresponding to the followingformula (I)

in which:

-   -   X represents a substituted boron atom chosen from the group        comprising B(OH)₂, B(OR)₂, BF₃M, B(OR′)₃M in which:        -   R is an alkyl group comprising 1 to 14 carbon atoms, an aryl            group, optionally substituted, or is such that (OR)₂ forms a            ring between the two oxygen atoms, (OR)₂ being in particular            chosen from the group comprising the bivalent radicals            deriving from diols, such as O—CH₂—CH₂—O, O—CH₂—CH₂—CH₂—O,            O—CH₂—C(CH₃)₂—CH₂—O, O—C(CH₃)₂—CH₂—CH₂—C(CH₃)₂—O,            O—CH(CH₃)—CH₂—CH₂—CH(CH₃)—O, O—CH(Ph)-CH(Ph)-O,            O—CH(CH₃)—CH₂—C(CH₃)₂—O, O-o-Ph-O, O—CH₂—CH₂—NH—CH₂—CH₂—O,            O—CH₂—CH₂—N(CH₂—CH₂—CH₂—CH₃)—CH₂—CH₂—O,            O—CH(COOH)—CH(COOH)—O and its esters, and the bivalent            radicals deriving from diacids, such as            OCO—CH₂—N(CH₃)—CH₂—COO,        -   R′ is an alkyl group comprising 1 to 14 carbon atoms or is            such that:            -   (OR′)₃ forms a ring between two of the oxygen atoms,                (OR′)₃ then being in the form OR′(OR)₂, where R′ is an                alkyl group comprising 1 to 14 carbon atoms and (OR)₂ is                as defined above, or            -   (OR′)₃ forms a bicycle between the three oxygen atoms,                (OR′)₃ being in particular chosen from the group                comprising the trivalent radicals deriving from triols,                such as H₃C—C—(CH₂—O)₃,        -   M represents the lithium Li⁺ ion, the sodium Na⁺ ion, the            potassium K⁺ ion, the caesium Cs⁺ ion, the ammonium            R^(c)R^(d)R^(e)R^(f)N⁺ ion where R^(c), R^(d) R², R^(f) are            chosen from H or a saturated carbon-containing chain            comprising in particular 1 to 6 carbon atoms chosen            independently of one another, and in particular X represents            B(OH)₂, B(OR)₂ or BF₃K,            R₁, R₄ and R₅, identical or different, are chosen from the            group constituted by:

1. H

2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;R₁ and R₄, or R₁ and R₅ being able to form a ring with 5, 6, or 7members optionally comprising a heteroatom chosen from oxygen, nitrogenand sulphur, said ring being able to be substituted;

R₂ is chosen from the group constituted by the groups being able to berepresented by R₁, R₄ or R₅, as well as —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted; R^(a) and R^(b)being able to be linked in order to form a ring, optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CH₂OH, —CH₂OR^(a),—CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH, —CR^(b)R^(b′)OR^(a),—CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, —OH, —OR^(a), —OZ′, —NH₂, —NHR^(a),—NR^(a)R^(b), —NHZ and —NZZ₂,

in which Z and Z₂ represent a protective group of an amine function, andZ′ represents a protective group of an alcohol function, andin which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;provided that:

-   -   when R₁, R₂, R₄ and R₅ represent H and B represents B(OH)₂,        B(OR)₂, or B(OR′)₃M, then    -   W is chosen from —COR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b),        —OH, —OR^(a) and —OZ′,    -   when R₁, R₂, R₄ and R₅ represent H and B represents BF₃M, then W        is chosen from —COOH, —COOR^(a), —CHO, —COR^(a)—CONH₂,        —CONHR^(a), —CONR^(a)R^(b), —OH, —OR^(a) and —OZ′,    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents        B(OH)₂, B(OR)₂, or B(OR′)₃M, then:        -   R₁ does not represent H, or        -   R₂ and R₄ do not represent H, or        -   R₂ and R₅ do not represent H.    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents BF₃M,        then R₁ or R₂ do not represent H.    -   when W represents —COOH or —COOR^(a), and B represents B(OH)₂,        B(OR)₂, or B(OR′)₃M, then:        -   R₁ does not represent H, or        -   R₂ and R₄ do not represent H, or        -   R₂ and R₅ do not represent H.

According to an advantageous embodiment, the present invention relatesto a compound in which W represents a functional group chosen from —CHO,—COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ.

According to an advantageous embodiment, the present invention relatesto a compound in which W represents a functional group chosen from —CHO,—COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a).

According to an advantageous embodiment, the present invention relatesto a compound in which W represents a functional group chosen from —CHO,—COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b).

According to an advantageous embodiment, the present invention relatesto a compound in which W represents a functional group chosen from—CONH—SO₂-cyclopropyl, —CH₂—NH—CO—CH₂—CH₃ and the group of the followingformula:

According to an advantageous embodiment, the present invention relatesto a compound in which R₂ represents H.

According to an advantageous embodiment, the present invention relatesto a compound in which R₂ is chosen from the group constituted by the—COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂groups, in which R^(a) and R^(b), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound in which R₁, R₄ and R₅ represent H, an aryl, aheterocycle, a heteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a compound in which R₁, R₂, R₄ and R₅ represent H.

According to an advantageous embodiment, the present invention relatesto a compound in which W represents a functional group chosen from —OH,—OR^(a), —OZ′, —NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂,

R₁, R₂, R₄ and R₅ representing in particular H.

According to an advantageous embodiment, the present invention relatesto a compound in which R₄ and R₅ represent H.

According to an advantageous embodiment, the present invention relatesto a compound in which R₁, R₄ and R₅ represent H.

According to an advantageous embodiment, the present invention relatesto a compound in which R₂, R₄ and R₅ represent H.

According to an advantageous embodiment, the present invention relatesto a compound in which R₁, R₂, R₄ and R₅ represent H.

According to an advantageous embodiment, the present invention relatesto a compound in which R₁ and R₂ represent, independently of oneanother, H or a linear, cyclic or branched alkyl group comprising 1 to15 carbon atoms, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound in which R₂ represents H or a linear, cyclic or branchedalkyl group comprising 1 to 15 carbon atoms, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound corresponding to the following formula (I-A)

in which:

-   -   X represents a substituted boron atom chosen from the group        comprising B(OH)₂, B(OR)₂, BF₃M, B(OR′)₃M in which:        -   R is an alkyl group comprising 1 to 14 carbon atoms, an aryl            group, optionally substituted, or is such that (OR)₂ forms a            ring between the two oxygen atoms, (OR)₂ being in particular            chosen from the group comprising the bivalent radicals            deriving from diols, such as O—CH₂—CH₂—O, O—CH₂—CH₂—CH₂—O,            O—CH₂—C(CH₃)₂—CH₂—O, O—C(CH₃)₂—CH₂—CH₂—C(CH₃)₂—O,            O—CH(CH₃)—CH₂—CH₂—CH(CH₃)—O, O—CH(Ph)-CH(Ph)-O,            O—CH(CH₃)—CH₂—C(CH₃)₂—O, O-o-Ph-O, O—CH₂—CH₂—NH—CH₂—CH₂—O,            O—CH₂—CH₂—N(CH₂—CH₂—CH₂—CH₃)—CH₂—CH₂—O,            O—CH(COOH)—CH(COOH)—O and its esters, and the bivalent            radicals deriving from diacids, such as            OCO—CH₂—N(CH₃)—CH₂—COO,        -   R′ is an alkyl group comprising 1 to 14 carbon atoms or is            such that:            -   (OR′)₃ forms a ring between two of the oxygen atoms,                (OR′)₃ then being in the form OR′(OR)₂, where R′ is an                alkyl group comprising 1 to 14 carbon atoms and (OR)₂ is                as defined above, or            -   (OR′)₃ forms a bicycle between the three oxygen atoms,                (OR′)₃ being in particular chosen from the group                comprising the trivalent radicals deriving from triols,                such as H₃C—C—(CH₂—O)₃,        -   M represents the lithium Li⁺ ion, the sodium Na⁺ ion, the            potassium K⁺ ion, the caesium Cs⁺ ion, the ammonium            R^(c)R^(d)R^(e)R^(f)N⁺ ion where R^(c), R^(d) R^(e), R^(f)            are chosen from H or a saturated carbon-containing chain            comprising in particular 1 to 6 carbon atoms chosen            independently of one another, and in particular X represents            B(OH)₂, B(OR)₂ or BF₃K,            R₁ and R₄, identical or different, are chosen from the group            constituted by:

1. H

2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;

at least one of the R₁ and R₄ groups representing H, R₂ is chosen fromthe group constituted by the groups being able to be represented by R₁or R₄, as well as —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b), —CN and —NO₂, in which R^(a) and R^(b), identical ordifferent, represent linear, cyclic or branched, aromatic, or aromaticor non-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1to 15 carbon atoms, optionally substituted; R^(a) and R^(b) being ableto be linked in order to form a ring, optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CONH—SO₂—R^(a), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, —CH₂—NH—COR^(a),

in which Z represents a protective group of an amine function, andin which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;provided that:

-   -   when R₁, R₂ and R₄ represent H and B represents B(OH)₂, B(OR)₂,        or B(OR′)₃M, then W is chosen from —COR^(a), —CONH₂, —CONHR^(a),        —CONR^(a)R^(b),    -   when R₁, R₂ and R₄ represent H and B represents BF₃M, then W is        chosen from —COOH, —COOR^(a), —CHO, —COR^(a)—CONH₂, —CONHR^(a),        —CONR^(a)R^(b),    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents        B(OH)₂, B(OR)₂, or B(OR′)₃M, then:        -   R₁ does not represent H, or        -   R₂ and R₄ do not represent H,    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents BF₃M,        then R₁ or R₂ do not represent H.    -   when W represents —COOH or —COOR^(a), and B represents B(OH)₂,        B(OR)₂, or B(OR′)₃M, then:        -   R₁ does not represent H, or        -   R₂ and R₄ do not represent H.

According to an advantageous embodiment, the present invention relatesto a compound corresponding to the following formula (I-B)

in which:

M represents the lithium Li⁺ ion, the sodium Na⁺ ion, the potassium K⁺ion, the caesium Cs⁺ ion, the ammonium R^(c)R^(d)R^(e)R^(f)N⁺ ion whereR^(c), R^(d) R^(e), R^(f) are chosen from H or a saturatedcarbon-containing chain comprising in particular 1 to 6 carbon atomschosen independently of one another,

BF₃M representing in particular BF₃K,

R₁ and R₄, identical or different, are chosen from the group constitutedby:

1. H

2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;at least one of the R₁ and R₄ groups representing H,

R₂ is chosen from the group constituted by the groups being able to berepresented by R₁ or R₄, as well as —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted,

—W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CONH—SO₂—R^(a), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, —CH₂—NH—COR^(a),

in which Z represents a protective group of an amine function, andin which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;provided that:

-   -   when R₁, R₂ and R₄ represent H, then W is chosen from —COOH,        —COOR^(a), —CHO, —COR^(a)—CONH₂, —CONHR^(a), —CONR^(a)R^(b),    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), then R₁ or R₂ do not        represent H.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which W represents afunctional group chosen from —CHO, —COR^(a), —COOH, —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CONH—SO₂—R^(a).

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which W represents afunctional group chosen from —CHO, —COR^(a), —COOH and —COOR^(a), Wrepresenting in particular —COOR^(a).

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which W represents afunctional group chosen from —CONH—SO₂-cyclopropyl, —CH₂—NH—CO—CH₂—CH₃and the group of the following formula:

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₂ represents H.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₂ is chosen from thegroup constituted by the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b) and —NO₂ groups, in which R^(a) and R^(b), identical ordifferent, represent linear, cyclic or branched, aromatic, or aromaticor non-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₁, R₂ and R₄ representH.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₁ represents H.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₁ represents H and R₄represents an aryl, a heterocycle, a heteroaryl or an alkyl as definedpreviously.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₄ represents H.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₄ represents H and R1represents an aryl, a heterocycle, a heteroaryl or an alkyl as definedpreviously.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₁ and R₂ represent Hand R₄ represents an aryl, a heterocycle, a heteroaryl or an alkyl asdefined previously.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₂ and R₄ represent Hand R₁ represents an aryl, a heterocycle, a heteroaryl or an alkyl asdefined previously.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₁ represents H, R₄represents an aryl, a heterocycle, a heteroaryl or an alkyl as definedpreviously, and R₂ is chosen from the group constituted by the —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups, in whichR^(a) and R^(b), identical or different, represent linear, cyclic orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₄ represents H, R₁represents an aryl, a heterocycle, a heteroaryl or an alkyl as definedpreviously, and R₂ is chosen from the group constituted by the —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups, in whichR^(a) and R^(b), identical or different, represent linear, cyclic orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-A) or (I-B) in which R₁ and R₄ represent H,and R₂ is chosen from the group constituted by the —COR^(a), —COOR^(a),—CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound corresponding to the following formula (I-C)

in which:

-   -   X represents a substituted boron atom chosen from the group        comprising B(OH)₂, B(OR)₂, BF₃M, B(OR′)₃M in which:        -   R is an alkyl group comprising 1 to 14 carbon atoms, an aryl            group, optionally substituted, or is such that (OR)₂ forms a            ring between the two oxygen atoms, (OR)₂ being in particular            chosen from the group comprising the bivalent radicals            deriving from diols, such as O—CH₂—CH₂—O, O—CH₂—CH₂—CH₂—O,            O—CH₂—C(CH₃)₂—CH₂—O, O—C(CH₃)₂—CH₂—CH₂—C(CH₃)₂—O,            O—CH(CH₃)—CH₂—CH₂—CH(CH₃)—O, O—CH(Ph)-CH(Ph)-O,            O—CH(CH₃)—CH₂—C(CH₃)₂—O, O-o-Ph-O, O—CH₂—CH₂—NH—CH₂—CH₂—O,            O—CH₂—CH₂—N(CH₂—CH₂—CH₂—CH₃)—CH₂—CH₂—O,            O—CH(COOH)—CH(COOH)—O and its esters, and the bivalent            radicals deriving from diacids, such as            OCO—CH₂—N(CH₃)—CH₂—COO,        -   R′ is an alkyl group comprising 1 to 14 carbon atoms or is            such that:            -   (OR′)₃ forms a ring between two of the oxygen atoms,                (OR′)₃ then being in the form OR′(OR)₂, where R′ is an                alkyl group comprising 1 to 14 carbon atoms and (OR)₂ is                as defined above, or            -   (OR′)₃ forms a bicycle between the three oxygen atoms,                (OR′)₃ being in particular chosen from the group                comprising the trivalent radicals deriving from triols,                such as H₃C—C—(CH₂—O)₃,        -   M represents the lithium Li⁺ ion, the sodium Na⁺ ion, the            potassium K⁺ ion, the caesium Cs⁺ ion, the ammonium            R^(c)R^(d)R^(e)R^(f)N⁺ ion where R^(c), R^(d) R², R^(f) are            chosen from H or a saturated carbon-containing chain            comprising in particular 1 to 6 carbon atoms chosen            independently of one another,        -   and in particular X represents B(OH)₂, B(OR)₂ or BF₃K,            R₁ and R₄, identical or different, are chosen from the group            constituted by:

1. H

2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;at least one of the R₁ and R₄ groups representing H,

R₂ is chosen from the group constituted by H and the —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted; R^(a) and R^(b) being able to be linked in orderto form a ring, optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b),

in which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;provided that:

-   -   when R₁, R₂ and R₄ represent H and B represents B(OH)₂, B(OR)₂,        or B(OR′)₃M, then W is chosen from —COR^(a), —CONH₂, —CONHR^(a),        —CONR^(a)R^(b),    -   when W represents —COOH or —COOR^(a), and B represents B(OH)₂,        B(OR)₂, or B(OR′)₃M, then:        -   R₁ does not represent H, or        -   R₂ and R₄ do not represent H.

According to an advantageous embodiment, the present invention relatesto a compound corresponding to the following formula (I-D)

in which:

M represents the lithium Li⁺ ion, the sodium Na⁺ ion, the potassium K⁺ion, the caesium Cs⁺ ion, the ammonium R^(c)R^(d)R^(e)R^(f)N⁺ ion whereR^(c), R^(d) R^(e), R^(f) are chosen from H or a saturatedcarbon-containing chain comprising in particular 1 to 6 carbon atomschosen independently of one another,

BF₃M representing in particular BF₃K,

R₁ and R₄, identical or different, are chosen from the group constitutedby:

1. H

2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;at least one of the R₁ and R₄ groups representing H,

-   -   R₂ is chosen from the group constituted by H and the —COR^(a),        —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups,        in which R^(a) and R^(b), identical or different, represent        linear, cyclic or branched, aromatic, or aromatic or        non-aromatic heterocyclic alkyl, alkenyl, alkynyl groups        comprising 1 to 15 carbon atoms, optionally substituted; R^(a)        and R^(b) being able to be linked in order to form a ring,        optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b),

in which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which W represents afunctional group chosen from —CHO, —COR^(a), —COOH and —COOR^(a), Wrepresenting in particular —COOR^(a).

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which R₂ represents H.

According to an advantageous embodiment, the present invention relatesto a process for the preparation of a compound of formula (I-C) or (I-D)in which R₂ is chosen from the group constituted by the —COOR^(a),—CONH₂, —CONHR^(a) and —CONR^(a)R^(b) groups, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which R₁, R₂ and R₄ representH. According to an advantageous embodiment, the present inventionrelates to a compound of formula (I-C) or (I-D) in which R₁ representsH.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which R₁ represents H and R₄represents an aryl, a heterocycle, a heteroaryl or an alkyl as definedpreviously.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which R₄ represents H.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which R₄ represents H and R₁represents an aryl, a heterocycle, a heteroaryl or an alkyl as definedpreviously.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which R₁ and R₂ represent Hand R₄ represents an aryl, a heterocycle, a heteroaryl or an alkyl asdefined previously.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which R₂ and R₄ represent Hand R₁ represents an aryl, a heterocycle, a heteroaryl or an alkyl asdefined previously.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which R₁ represents H, R₄represents an aryl, a heterocycle, a heteroaryl or an alkyl as definedpreviously, and R₂ is chosen from the group constituted by the —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups, in whichR^(a) and R^(b), identical or different, represent linear, cyclic orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which R₄ represents H, R₁represents an aryl, a heterocycle, a heteroaryl or an alkyl as definedpreviously, and R₂ is chosen from the group constituted by the —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups, in whichR^(a) and R^(b), identical or different, represent linear, cyclic orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound of formula (I-C) or (I-D) in which R₁ and R₄ represent H,and R₂ is chosen from the group constituted by the —COR^(a), —COOR^(a),—CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups, in which R^(a) andR^(b), identical or different, represent linear, cyclic or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a compound chosen from the group constituted by the compounds of thefollowing formula and their enantiomer:

According to an advantageous embodiment, the present invention relatesto a compound chosen from the group constituted by the compounds of thefollowing formulae and their enantiomers:

The invention also relates to the use of a compound of formula (I), forthe preparation of compounds of the following formula (II):

in which:

R₁, R₃, R₄ and R₅, identical or different, are chosen from the groupconstituted by:

1. H, provided that R₃ does not represent H,2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;R₁ and R₄, or R₁ and R₅ being able to form a ring with 5, 6, or 7members optionally comprising a heteroatom chosen from oxygen, nitrogenand sulphur, said ring being able to be substituted;

R₂ is chosen from the group constituted by the groups being able to berepresented by R₁, R₄ or R₅, as well as —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CH₂OH, —CH₂OR^(a),—CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH, —CR^(b)R^(b′)OR^(a),—CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, —OH, —OR^(a), —OZ′, —NH₂, —NHR^(a),—NR^(a)R^(b), —NHZ and —NZZ₂,

in which Z represents a protective group of an amine function, Z′represents a protective group of an alcohol function, andin which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;provided that:

-   -   when R₁, R₂, R₄ and R₅ represent H and B represents B(OH)₂,        B(OR)₂, or B(OR′)₃M, then W is chosen from —COR^(a), —CONH₂,        —CONHR^(a), and —CONR^(a)R^(b),    -   when R₁, R₂, R₄ and R₅ represent H and B represents BF₃M, then W        is chosen from —COOH, —COOR^(a), —CHO, —COR^(a)—CONH₂,        —CONHR^(a), —CONR^(a)R^(b),    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents        B(OH)₂, B(OR)₂, or B(OR′)₃M, then:    -   R₁ does not represent H, or    -   R₂ and R₄ do not represent H, or    -   R₂ and R₅ do not represent H.    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents BF₃M,        then R₁ or R₂ do not represent H.    -   when W represents —COOH or —COOR^(a), and B represents B(OH)₂,        B(OR)₂, or B(OR′)₃M, then:    -   R₁ does not represent H, or    -   R₂ and R₄ do not represent H, or    -   R₂ and R₅ do not represent H,        by reaction of said compound of formula (I) with a compound of        the following formula (III):

R₃—X₂,

in which R₃ is as defined above, and X₂ is chosen from the groupconstituted by the halides, in particular iodine, bromine and chlorine,and triflate (OTf), in the presence of a catalyst containing atransition metal, and, optionally, a ligand.

According to an advantageous embodiment, the present invention relatesto a use in which said transition metal is palladium (0) or palladium(II), said catalyst being in particular chosen from the groupconstituted by Pd(PPh₃)₄, Pd(OAc)₂, PdCl₂(dppf), PdCl₂ and PdCl₂(CN)₂.

According to an advantageous embodiment, the present invention relatesto a use, said use being in the presence of a ligand chosen from thegroup constituted by PPh₃, P(tBu)₃, n-BuPAd₂,1,2-bis(diphenylphosphine)propane (dpp), tricyclohexylphosphane (PCy₃),S-Phos and Xantphos.

According to an advantageous embodiment, the present invention relatesto a use in which W represents a functional group chosen from —CHO,—COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)H,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ.

According to an advantageous embodiment, the present invention relatesto a use in which W represents a functional group chosen from—CONH—SO₂-cyclopropyl, —CH₂—NH—CO—CH₂—CH₃, and the group of thefollowing formula:

According to an advantageous embodiment, the present invention relatesto a use in which R₂ represents H.

According to an advantageous embodiment, the present invention relatesto a use in which R₂ is chosen from the group constituted by the groups—COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂,in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto a use in which R₁, R₄ and R₅ represent H, an aryl, a heterocycle, aheteroaryl or an alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto a use in which R₁, R₂, R₄ and R₅ represent H.

According to an advantageous embodiment, the present invention relatesto a use in which W represents a functional group chosen from —OH,—OR^(a), —OZ′, —NH₂, —NHR^(a), —NR^(a)R^(b), —NHZ and —NZZ₂,

R₁, R₂, R₄ and R₅ representing in particular H.

According to an advantageous embodiment, the present invention relatesto a use in which R₁ and R₂ represent, independently of one another, Hor a linear, cyclic or branched alkyl group comprising 1 to 15 carbonatoms, optionally substituted.

According to an advantageous embodiment, the present invention relatesto a use in which R₂ represents H or a linear, cyclic or branched alkylgroup comprising 1 to 15 carbon atoms, optionally substituted.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) as described previously, forthe preparation of compounds of the following formula (II-A):

in which:

R₁, R₃ and R₄, identical or different, are chosen from the groupconstituted by:

1. H, provided that R₃ does not represent H,2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;at least one of the R₁ and R₄ groups representing H,

R₂ is chosen from the group constituted by the groups being able to berepresented by R₁, R₄ or R₅, as well as —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CONH—SO₂—R^(a), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, —CH₂—NH—COR^(a),

in which Z represents a protective group of an amine function, andin which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;provided that:

-   -   when R₁, R₂ and R₄ represent H and B represents B(OH)₂, B(OR)₂,        or B(OR′)₃M, then W is chosen from —COR^(a), —CONH₂, —CONHR^(a),        —CONR^(a)R^(b),    -   when R₁, R₂ and R₄ represent H and B represents BF₃M, then W is        chosen from —COOH, —COOR^(a), —CHO, —COR^(a)—CONH₂, —CONHR^(a),        —CONR^(a)R^(b),    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents        B(OH)₂, B(OR)₂, or B(OR′)₃M, then:        -   R₁ does not represent H, or        -   R₂ and R₄ do not represent H,    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents BF₃M,        then R₁ or R₂ does not represent H.    -   when W represents —COOH or —COOR^(a), and B represents B(OH)₂,        B(OR)₂, or B(OR′)₃M, then:        -   R₁ does not represent H, or        -   R₂ and R₄ do not represent H,            by reaction of said compound of formula (I) with a compound            of the following formula (III):

R₃—X₂,

in which R₃ is as defined above, and X₂ is chosen from the groupconstituted by the halides, in particular iodine, bromine and chlorine,and triflate (OTf), in the presence of a catalyst containing atransition metal, and, optionally, of a ligand.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-B) as described previously, forthe preparation of compounds of the following formula (II-A):

in which:

R₁, R₃ and R₄, identical or different, are chosen from the groupconstituted by:

1. H, provided that R₃ does not represent H,2. the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted;3. the heterocycles or heteroaryls comprising rings with 2 to 15 carbonatoms, optionally substituted;4. the linear or branched alkenyls comprising 1 to 12 carbon atoms,optionally substituted, or carbon rings comprising 3 to 12 carbon atomsand one or more C═C double bonds, optionally substituted;5. the linear or branched alkynyls comprising 1 to 15 carbon atoms,optionally substituted;6. the linear, cyclic or branched alkyl groups comprising 1 to 15 carbonatoms, optionally substituted;at least one of the R₁ and R₄ groups representing H,

R₂ is chosen from the group constituted by the groups being able to berepresented by R₁, R₄ or R₅, as well as —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted,

W represents a functional group chosen from —CHO, —COR^(a), —COOH,—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CONH—SO₂—R^(a), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, —CH₂—NH—COR^(a),

in which Z represents a protective group of an amine function, andin which R^(a), R^(b) and R^(b′), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;provided that:

-   -   when R₁, R₂ and R₄ represent H and B represents BF₃M, then W is        chosen from —COOH, —COOR^(a), —CHO, —COR^(a)—CONH₂, —CONHR^(a),        —CONR^(a)R^(b),    -   when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),        —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents BF₃M,        then R₁ or R₂ do not represent H,        by reaction of said compound of formula (I) with a compound of        the following formula (III):

R₃—X₂,

in which R₃ is as defined above, and X₂ is chosen from the groupconstituted by the halides, in particular iodine, bromine and chlorine,and triflate (OTf), in the presence of a catalyst containing atransition metal, and, optionally, of a ligand.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which saidtransition metal is palladium (0) or palladium (II), said catalyst beingin particular chosen from the group constituted by Pd(PPh₃)₄, Pd(OAc)₂,PdCl₂(dppf), PdCl₂ and PdCl₂(CN)₂.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B), said use being inthe presence of a ligand chosen from the group constituted by PPh₃,P(tBu)₃, n-BuPAd₂, 1,2-bis(diphenylphosphine)propane (dpp),tricyclohexylphosphane (PCy₃), S-Phos and Xantphos.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which W representsa functional group chosen from —CHO, —COR^(a), —COOH, —COOR^(a), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH and—CR^(b)R^(b′)OR^(a).

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which W representsa functional group chosen from —CHO, —COR^(a), —COOH and —COOR^(a), Wrepresenting in particular —COOR^(a).

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which W representsa functional group chosen from —CONH—SO₂-cyclopropyl,—CH₂—NH—CO—CH₂—CH₃, and the group of the following formula:

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₂represents H.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₂ is chosenfrom the group constituted by the —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₁, R₂ andR₄ represent H.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₁represents H.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₁represents H and R₄ represents an aryl, a heterocycle, a heteroaryl oran alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₄represents H.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₄represents H and R1 represents an aryl, a heterocycle, a heteroaryl oran alkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₁ and R₂represent H and R₄ represents an aryl, a heterocycle, a heteroaryl or analkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₂ and R₄represent H and R₁ represents an aryl, a heterocycle, a heteroaryl or analkyl as defined previously.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₁represents H, R₄ represents an aryl, a heterocycle, a heteroaryl or analkyl as defined previously, and R₂ is chosen from the group constitutedby the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂groups, in which R^(a) and R^(b), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₄represents H, R₁ represents an aryl, a heterocycle, a heteroaryl or analkyl as defined previously, and R₂ is chosen from the group constitutedby the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂groups, in which R^(a) and R^(b), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted;

R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B) in which R₁ and R₄represent H, and R₂ is chosen from the group constituted by the—COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b) and —NO₂ groups,

in which R^(a) and R^(b), identical or different, represent linear,cyclic or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms,optionally substituted;R^(a) and R^(b) being able to be linked in order to form a ring,optionally substituted.

According to an advantageous embodiment, the present invention relatesto the use of a compound of formula (I-A) or (I-B), respectively ofparticular formula (I-C) or (I-D) as defined previously.

According to an advantageous embodiment, the present invention relatesto a use in which R₃ represents a group chosen from:

According to an advantageous embodiment, the present invention relatesto a use in which R₃ represents a group chosen from:

According to an advantageous embodiment, the present invention relatesto the use of a compound chosen from the group constituted by thecompounds of the following formulae and their enantiomers:

The following examples illustrate the invention.

EXAMPLES Example 1 Synthesis ofpotassium[2-ethoxycarbonylcyclopropyl]-trifluoroborate

Potassium vinyl trifluoroborate (888 g, 6.63 mole) is solubilized in THF(9 L). Palladium acetate (14.88 g, 66 mmol) is added. The mixture isheated to 35° C. and a solution of diazo ethyl acetate (902 ml, 7.72mole) in THF (1 L) is added dropwise over 3 hours 40 (exothermicity).The mixture is stirred for an additional 30 minutes. Heptane is added tothe solution. The suspension thus obtained is stirred for 30 minutes,then filtered. The solid is crystallized from 9 L of acetone at −18° C.The solid is filtered and dried in order to produce the expected cisproduct (335 g, 1.52 mole, 23%). The filtrate is washed with bone black,filtered and concentrated to dryness. The product is crystallized from10 L of ethanol in order to produce the expected trans product (903 g,4.1 mmol, 62%).

¹H-NMR (DMSO-d₆, 300 MHz) δ 3.96 (q, J=7.1 Hz, 2H), 1.15 (t, J=7.1 Hz,3H), 1.10 (m, 1H), 0.63 (m, 1H), 0.47 (m, 1H), −0.06 (m, 1H).

¹H-NMR (DMSO-d₆, 300 MHz) δ 3.90 (q, J=7.0 Hz, 2H), 1.25 (m, 1H), 1.12(t, J=7.0 Hz, 3H), 0.75 (m, 1H), 0.54 (m, 1H), −0.15 (m, 1H).

Example 2 Synthesis of substituted potassium[2-ethoxycarbonylcyclopropyl]-trifluoroborates

General Procedure:

Method A: Palladium acetate (0.01-0.2 eq.) is added under nitrogen to asolution of potassium alkenyltrifluoroborate (1 eq.) in tetrahydrofuran.The mixture is heated to 35-70° C. and a solution of diazo ethyl acetate(1.2 to 5 eq.) in tetrahydrofuran is added very slowly dropwise. Thereaction medium is stirred at this temperature for 1 to 10 h untilconversion is complete. Heptane is added to the solution. The suspensionthus obtained is stirred for 30 minutes, then filtered. When the cisderivative sufficiently abundant in the crude reaction medium, it can becrystallized from acetone at low temperature (−20° C.). As regards thetrans compound it is crystallized from an acetonitrile/diethyl ethermixture.

Method B: Copper acetoacetate (0.2 eq.) is added under nitrogen to asolution of potassium alkenyltrifluoroborate (1 eq.) in atoluene/dioxane mixture 1/1. The mixture is heated to 35-70° C. and asolution of diazo ethyl acetate (1.2 to 5 eq.) in toluene is added veryslowly dropwise. The reaction medium is stirred at this temperature for1 to 10 h until conversion is complete. After returning to ambienttemperature, heptane is added to the solution. The suspension thusobtained is stirred for 30 minutes, then filtered. When the cisderivative is sufficiently abundant in the crude reaction medium, it canbe crystallized from acetone at low temperature (−20° C.). As regardsthe trans compound, it is crystallized from an acetonitrile/diethylether mixture or methanol.

Synthesis ofpotassium[2-ethoxycarbonyl-3-methyl-cyclopropyl]-trifluoroborate

The product is obtained according to the general procedure.

¹H-NMR (DMSO-d₆, 300 MHz) (trans compound): δ 3.87 (q, J=7.1 Hz, 2H),1.3-1.0 (m, 2H), 1.09 (t, J=7.1 Hz, 3H), 0.95 (d, J=7.9 Hz, 3H), −0.30(m, 1H).

¹H-NMR (DMSO-d₆, 300 MHz) (cis compound): δ 3.96 (q, J=7.05 Hz, 2H),1.3-1.0 (m, 2H), 1.15 (t, J=7.05 Hz, 3H), 0.90 (d, J=5.3 Hz, 3H), −0.16(m, 1H).

Synthesis ofpotassium[2-ethoxycarbonyl-1-methyl-cyclopropyl]-trifluoroborate

The product is obtained according to the general procedure.

¹H-NMR (DMSO-d₆, 300 MHz) (trans compound): δ 3.9 (m, 2H), 1.28 (dd,J=4.7 Hz, J=7.1 Hz, 1H), 1.14 (t, J=7.1 Hz, 3H), 0.87 (s, 3H), 0.63 (dd,J=1.9 Hz, J=7.1 Hz, 1H), 0.45 (m, 1H).

No visible cis compound.

Synthesis of potassium[2-ethoxycarbonyl-3-cyclopropyl-cyclopropyl]-trifluoroborate

The product is obtained according to the general procedure.

Synthesis ofpotassium[2-ethoxycarbonyl-3-propyl-cyclopropyl]-trifluoroborate

¹H-NMR (DMSO-d₆, 300 MHz) (trans compound): δ 3.95 (q, J=6.6 Hz, 2H),1.5-1.0 (m, 9H), 0.83 (t, J=6.6 Hz, 3H), −0.11 (m, 1H).

¹H-NMR (DMSO-d₆, 300 MHz) (cis compound): δ 3.88 (q, J=7.1 Hz, 2H),1.5-1.0 (m, 9H), 0.86 (d, J=7.1 Hz, 3H), −0.26 (m, 1H).

Synthesis ofpotassium[2-ethoxycarbonyl-3-phenyl-cyclopropyl]-trifluoroborate

The product is obtained according to the general procedure.

¹H-NMR (DMSO-d₆, 300 MHz) (trans compound): δ 7.20-7.0 (m, 5H), 3.73 (m,2H), 2.18 (t, J=8.6 Hz, 1H), 1.56 (dd, J=8.4 Hz, J=6.6 Hz, 1H), 0.92 (t,J=8.8 Hz, 3H), 0.71 (m, 1H).

¹H-NMR (DMSO-d₆, 300 MHz) (cis compound): δ 7.20-7.0 (m, 5H), 3.94 (q,J=6.4 Hz, 2H), 2.29 (m, 1H), 1.59 (m, 1H), 1.09 (t, J=6.4 Hz, 3H), 0.37(m, 1H).

Synthesis ofpotassium[2-ethoxycarbonyl-1-phenyl-cyclopropyl]-trifluoroborate

The product is obtained according to the general procedure.

MS (ES-, MeOH): 257.2 [M]−

Example 3 Synthesis of potassium cyclopropyltrifluoroborates substitutedin position 2

General Method:

Catalyst Pd(OAc)₂ or Cu(acac)₂ (0.02-0.2 eq.) is added to a solution ofpotassium vinyltrifluoroborate (1 eq) in THF or a toluene/dioxanemixture. The reaction medium is heated to 40-70° C. then the diazoderivative (2-5 eq.) is added slowly dropwise. The medium is stirred atthis temperature for 1-10 h until conversion is complete. Afterreturning to ambient temperature, heptane is added to the solution. Thesuspension thus obtained is stirred for 30 minutes, then filtered. Whenthe cis derivative is sufficiently abundant in the crude reactionmedium, it can be crystallized from acetone at low temperature (−20°C.). As regards the trans compound, it is crystallized from anacetonitrile/diethyl ether mixture or methanol.

Synthesis of potassium[2-benzyloxycarbonylcyclopropyl]-trifluoroborate

The product is obtained according to the general procedure.

¹H-NMR (DMSO-d₆, 300 MHz) (trans compound) δ 7.41-7.25 (m, 5H), 5.0 (d,J=1.8 Hz, 2H), 1.16 (m, 1H), 0.69 (dm, J=9.7 Hz, 1H), 0.53 (td, J=7.3Hz, J=1.8 Hz, 1H), 0.00 (m, 1H).

¹H-NMR (DMSO-d₆, 300 MHz) (cis compound) δ 7.41-7.25 (m, 5H), 4.94 (d,J=12.1 Hz, 2H), 1.34 (m, 1H), 0.82 (m, 1H), 0.22 (tm, J=7.9 Hz, 1H),−0.08 (m, 1H).

Synthesis of potassium[2-tert-butoxycarbonylcyclopropyl]-trifluoroborate

The product is obtained according to the general procedure.

¹H-NMR (DMSO-d₆, 300 MHz) (trans compound) δ 1.36 (s, 9H), 1.01 (m, 1H),0.54 (dm, J=9.9 Hz, 1H), 0.40 (tm, J=6.6 Hz, 1H), −0.11 (m, 1H).

¹H-NMR (DMSO-d₆, 300 MHz) (cis compound) δ 1.33 (s, 9H), 1.15 (m, 1H),0.68 (m, 1H), 0.47 (m, 1H), −0.21 (m, 1H).

Synthesis ofpotassium[2,2-bis(ethoxycarbonyl)cyclopropyl]-trifluoroborate

The product is obtained according to the general procedure.

¹H-NMR (DMSO-d₆, 300 MHz) δ 4.2 (q, 2H, J=7.1 Hz), 3.99 (q, 2H, J=8 Hz),1.22 (t, 3H, J=8 Hz), 1.13 (t, 3H, J=7.1 Hz), 1.02 (dd, 1H, J=9.5 Hz,J=1.7 Hz), 0.83 (dm, H, J=10.3 Hz), 0.54 (m, 1H).

Synthesis of potassium[2-ethoxycarbonyl-2-(pyrrolidine-1-carbonyl)cyclopropyl]-trifluoroborate

The product is obtained according to the general procedure.

¹H-NMR (DMSO-d₆, 300 MHz) cis/trans mixture δ 3.97 (m, 4H), 3.27-3.49(m, 8H), 0.98-1.24 (m, 12H), 1.09 (t, 3H, J=8.5 Hz), 0.77 (m, 2H), 0.58(m, 1H), 0.39 (m, 1H).

Example 4 Synthesis of(trans)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclopropanecarboxylicacid

The potassium trifluoroborate derivative (Example 1, 15 g, 68.2 mmol) issolubilized in THF (150 ml). Trimethylsilane chloride (18.2 g, 143.2mmol) is added dropwise. The medium is stirred at ambient temperaturefor 30 minutes. The reaction medium is poured into 600 ml of water. TheTHF is concentrated with a rotary evaporator and a molar solution ofsodium hydroxide is added until a basic pH is reached (approximately 50ml). The medium is stirred at ambient temperature overnight. NaOH inpellets (2 g) and a solution of sodium hydroxide (6N) are added and themedium is stirred overnight. The medium is concentrated to dryness,taken up in 700 ml of toluene and pinacol (8.46 g, 71.6 mmol) is added.The medium is filtered on Celite and concentrated to dryness. Theamorphous oil is triturated in pentane (50 ml) in order to obtain awhite solid (2.85 g, 13.4 mmol). The filtrate is placed in the freezerin order to produce a second batch of product (5.8 g, 27.4 mmol, overallyield 60%). ¹H-NMR (DMSO-d₆, 300 MHz) δ 12.25 (bs, 1H), 1.51 (m, 1H),1.17 (s, 12H), 1.04 (m, 1H), 0.84 (m, 1H), 0.30 (m, 1H).

Example 5 Synthesis ofpotassium[(trans)-2-methylcyclopropyl]trifluoroborate

Carboxylic acid (Example 4, 8.65 g, 40.8 mmol) is solubilized in THF(216 ml). The medium is cooled down to 0° C. and triethylamine is added(8.5 ml, 61.2 mmol). Then ethylchloroformate (6.64 g, 61.2 mmol) isadded dropwise. The medium is stirred at ambient temperature for 1 hour,cooled down to 0° C. and a solution of sodium azide (132.6 g, 2.04 mole)in water (325 ml) is added dropwise. The medium is stirred at ambienttemperature overnight. Water (200 ml) is added and the expected productis extracted twice with isopropyl ether. The organic phase is dried overmagnesium sulphate and filtered. Toluene (50 ml) and benzyl alcohol (4.3ml) are added and the medium is heated to 105° C. The THF and isopropylether are distilled off from the medium. After being left overnight at105° C., the medium is concentrated to dryness. The crude reactionmedium is purified twice by chromatography on silica gel which does notallow removal of the excess benzyl alcohol. The product (6.48 g) is thenput back in a water (16.2 ml)/methanol (78 ml) mixture and KHF₂ (11.17g) is added and the medium is stirred at ambient temperature overnight.The suspension is concentrated to dryness and the solid is triturated inacetonitrile to 90° C. for 4 hours. The filtrate is concentrated inorder to produce a white solid. ¹H-NMR (DMSO-d₆, 300 MHz) δ 7.33 (m,5H), 6.99 (bd, 0.8H), 6.7 (bs, 0.2H), 4.96 (s, 2H), 2.16 (m, 1H), 0.12(m, 1H), 0.0 (m, 1H), −0.52 (m, 1H).

Example 6 Synthesis ofpotassium[(trans)-2-carboxycyclopropyl]-trifluoroborate

Palladium on carbon (0.2 mmol, 0.2 eq.) is added under an inertatmosphere to a solution of ester (Example 3, 1 mmol) in 5 ml ofmethanol. The reaction medium is placed under a hydrogen atmosphere (1atm) for 5 hours, filtered on frit then concentrated to dryness in orderto produce the expected carboxylic acid.

¹H-NMR (DMSO-d₆, 300 MHz) (trans compound) δ 1.12 (m, 1H), 0.68 (d,J=10.0 Hz, 1H), 0.52 (t, J=7.3 Hz, 1H), 0.00 (m, 1H).

Example 10 Synthesis of [(trans)-2-ethoxycarbonylcyclopropyl]boronicacid

Silica gel (1 eq.) is added to a solution of potassium trifluoroboratederivative (Example 1, 1 eq.) in water. The reaction medium is stirredat ambient or high temperature for 4 h then filtered on frit. Theaqueous phase is extracted 3 times with ethyl acetate. The combinedorganic phases are washed with salt water, dried over magnesium sulphateand concentrated to dryness in order to produce the expected boronicacid derivative.

¹H-NMR (DMSO-d₆, 300 MHz) (trans compound) δ 4.03 (t, J=7.4 Hz, 2H),1.58 (m, 1H), 1.17 (t, J=7.4 Hz, 3H), 0.97 (m, 1H), 0.87 (td, J=7.5 Hz,J=2.7 Hz, 1H), 0.30 (m, 1H).

Example 11 Synthesis of [(trans)-2-ethoxycarbonylcyclopropyl]boronicacid MIDA ester

N-methyliminodiacetic acid (1 eq.) is added to a solution of boronicacid derivative (Example 10, 1 eq.) in a toluene/DMSO mixture. Thereaction medium is heated under reflux with a Dean-Stark apparatus untilthe starting product has completely disappeared. After returning toambient temperature, the medium is hydrolyzed by the addition of waterand extracted 3 times with a THF/Et₂O mixture 2/1. The organic phasesare dried over magnesium sulphate, filtered on frit and concentrated todryness in order to produce a crude reaction medium. Purification bychromatography on silica (eluent: Heptane/AcOEt) produces the expectedderivative.

¹H-NMR (DMSO-d₆, 300 MHz) (trans compound) δ 4.21 (dd, J=16.9 Hz, J=4.7Hz, 2H), 4.03 (m, 4H), 2.95 (s, 3H), 1.37 (m, 1H), 1.16 (t, J=7.1 Hz,3H), 0.96 (m, 1H), 0.68 (td, J=7.6 Hz, J=3.1 Hz, 1H), 0.42 (m, 1H).

Example 13 Synthesis of vinyloxymethylbenzene

Benzyl alcohol (5.18 mL, 50.0 mmol) and vinyl acetate (9.22 mL, 100mmol, 2.0 equiv) are added to a suspension of [Ir(cod)Cl]₂ (336 mg,0.500 mmol, 1 mol %) and Na₂CO₃ (3.18 g, 30.0 mmol, 0.6 equiv) intoluene (50 mL). After stirring for 2 hours at 100° C., the mixtureobtained is cooled down to ambient temperature and filtered on Celite.The filtrate is concentrated under reduced pressure and the residuepurified by flash chromatography on silica gel (petroleum ether/EtOAc:98/2) in order to produce a yellow oil (5.15 g, 77%).

¹H-NMR (CDCl₃, 400 MHz) δ 7.39-7.29 (m, 5H), 6.57 (dd, J=14.3 Hz andJ=6.8 Hz, 1H), 4.76 (s, 2H), 4.30 (dd, J=14.3 Hz and J=2.0 Hz, 1H), 4.08(dd, J=6.8 Hz and J=2.0 Hz, 1H).

Example 14 Synthesis of2-[(E)-2-benzyloxy)ethenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2)

4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane (84.8 μL, 0.500 mmol)and the ruthenium catalyst [Ru]-1 (prepared by reaction of Grubbs Icatalyst with 1-propanol and Et₃N in toluene at 75° C. for 16 h,according to Dinger, M. B.; Mol, J. C. Organometallics 2003, 22,1089-1095) (3.63 mg, 5.00 μmol, 1 mol %) are added to a solution ofbenzyl vinyl ether (Example 13, 201 mg, 1.50 mmol, 3.0 equiv) in benzene(5.0 mL) After stirring for 24 hours at 100° C., the mixture obtained iscooled down to ambient temperature, concentrated under reduced pressureand the residue purified by flash chromatography on silica gel(petroleum ether/EtOAc: 90/10) in order to produce a yellow oil.

IR 1632, 1607, 1367, 1309, 1124, 1104, 970, 851, 814, 736, 696, 656cm-¹; ¹H-NMR (CDCl₃, 400 MHz) δ 7.36-7.29 (m, 5H), 7.15 (d, J=14.4 Hz,1H), 4.83 (s, 2H), 4.56 (d, J=14.3 Hz, 1H), 1.26 (s, 12H); ¹³C-NMR (100MHz, CDCl₃) δ 162.7 (d), 136.4 (s), 128.5 (d), 128.0 (d), 127.6 (d),82.7 (s, 2C), 70.6 (t), 24.7 (q, 4C); EI-MS m/z (relative intensity) 260(M^(+), 0.3), 160 (2), 133 (M-Bpin⁺, 2), 117 (2), 116 (13), 92 (11), 91(100), 85 (3), 84 (6), 83 (8), 69 (2), 65 (8), 59 (2), 57 (2), 55 (2).HRMS calcd for C₁₅H₂₁BO₃Na (M+Na⁺): 283.14760. Found: 283.14798.

Example 15 Synthesis of (2R*)-2-(benzyloxy)-1,1-dibromocyclopropane

Potash (24.8 g, 442 mmol, 14.4 equivalents), tetrabutylammonium sulphate(3.13 g, 9.21 mmol, 0.3 equivalents) then tribromomethane (24.7 mL, 282mmol, 9.2 equivalents) are added successively to a solution of vinylbenzoate (Example 13, 4.12 g, 30.7 mmol) in dichloromethane (250 mL) at0° C. After stirring for 2 hours at ambient temperature, the reactionmedium is filtered on celite, rinsed with dichloromethane, then 400 mlof water is added to the filtrate. The phases are separated and theaqueous pxhase is extracted with diethyl ether. The combined organicphases are dried over magnesium sulphate, filtered then evaporated todryness under reduced pressure. The crude reaction medium is purified bychromatography on silica gel (Eluent: petroleum ether/AcOEt: 98/2) inorder to produce 8.73 g (93%) of Compound 4 in the form of an orangeoil.

¹H NMR (400 MHz, CDCl₃) δ 7.44-7.31 (m, 5H), 4.90 (d, AB syst, J=11.2Hz, 1H), 4.68 (d, AB syst, J=11.2 Hz, 1H), 3.63 (dd, J=8.1 Hz and J=5.0Hz, 1H), 1.87 (dd, J=8.9 Hz and J=8.2 Hz, 1H), 1.75 (dd, J=8.9 Hz andJ=5.0 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 136.4 (s), 128.6 (d, 2C),128.4 (d, 2C), 128.3 (d), 73.4 (t), 62.9 (d), 29.8 (t), 26.8 (s).

Example 16 Synthesis of ((trans)-1-(benzyloxy)-2-bromocyclopropane

n-Butyllithium (860 μL, 2.5 M in hexane, 2.14 mmol, 1.2 equivalents) isadded dropwise to a solution of dibromo-cyclopropane (Example 15, 546mg, 1.78 mmol) in THF (10 mL) at −78° C. After stirring for 10 minutesat −78° C., 4 ml of methanol is added. The reaction medium is stirredfor 15 minutes then left to return to ambient temperature. Afterstirring for 30 minutes at this temperature, water (10 mL) and diethylether (10 mL) are added, then the aqueous phase is extracted withdiethyl ether. The combined organic phases are dried over magnesiumsulphate, filtered then evaporated to dryness under reduced pressure.The crude reaction medium is purified by chromatography on silica gel(petroleum ether/AcOEt: 98/2) in order to produce 334 mg (82%) ofcompound 6 in the form of a yellow oil.

¹H NMR (400 MHz, CDCl₃) δ 7.39-7.30 (m, 5H), 4.61 (d, AB syst, J=11.7Hz, 1H), 4.57 (d, AB syst, J=11.7 Hz, 1H), 3.56 (ddd, J=7.4 Hz, J=3.9 Hzand J=1.7 Hz, 1H), 2.93 (ddd, J=8.9 Hz, J=5.0 Hz and J=1.7 Hz, 1H), 1.38(ddd, J=8.9 Hz, J=7.8 Hz and J=3.9 Hz, 1H), 1.09 (ddd, apparent td,J=7.5 Hz and J=5.0 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 137.1 (s), 128.5(d, 2C), 128.1 (d, 2C), 128.0 (d), 73.0 (t), 59.9 (d), 17.8 (d), 17.7(t)

Example 17 Synthesis of2-[(trans)-2-(benzyloxy)cyclopropyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Starting from Example 14: Diethylzinc (450 μL, 1 M in hexane, 0.448mmol, 2.0 equivalents) then chloroiodomethane (65.3 μL, 0.896 mmol, 4.0equivalents) are added to a solution of vinyl ether (Example 14, 58.3mg, 0.224 mmol) in dichloromethane (2.5 mL) at 0° C. After 1.5 hours at0° C., the reaction is hydrolyzed by the addition of a saturated aqueoussolution of ammonium chloride (10 mL) then the aqueous phase isextracted with dichloromethane (10 mL). The combined organic phases aredried over magnesium sulphate, filtered then evaporated to dryness underreduced pressure. The residue is purified by chromatography on silicagel (Eluent: petroleum ether/AcOEt: 90/10) in order to produce 39.7 mg(65%) of Compound 3 in the form of a colourless oil.

Starting from Example 15: n-Butyllithium (144 μL, 2.5 M in hexane, 0.360mmol, 1.2 equivalents) is added to a solution of dibromocyclopropane(Example 15, 91.8 mg, 0.300 mmol) in THF (3.0 mL) at −78° C. After 15minutes at −78° C., pinacolborane (600 μL, 1 M in THF, 2.0 equivalents)is added and the reaction mixture is heated at 50° C. for 16 hours. Thereaction is then cooled down to ambient temperature then hydrolyzed bythe addition of a saturated aqueous solution of ammonium chloride. Theaqueous phase is extracted with diethyl ether then the combined organicphases are dried over magnesium sulphate, filtered and evaporated todryness under reduced pressure. The residue is purified bychromatography on silica gel (Eluent: petroleum ether/AcOEt: 90/10) inorder to produce Compound 3 in the form of a pale yellow oil.

Starting from Example 16: t-Butyllithium (23.3 mL, 1.7 M in hexane, 39.6mmol, 2.0 equivalents) is added to a solution of bromocyclopropane(Example 16, 4.50 g, 19.8 mmol) in diethyl ether (120 mL) at −78° C.After 30 minutes at this temperature, pinacol isopropoxyboronate (12.1mL, 59.4 mmol, 3.0 equivalents) is added dropwise then the reactionmedium is left to slowly return to ambient temperature for 2 hours.After 30 minutes at this temperature, the medium is hydrolyzed by theaddition of a saturated aqueous solution of ammonium chloride (150 mL),the phases are separated then the aqueous phase is extracted withdiethyl ether. The combined organic phases are dried over magnesiumsulphate, filtered then evaporated to dryness under reduced pressure.The residue is purified by chromatography on silica gel (Eluent:petroleum ether/AcOEt: 90/10) in order to produce 4.51 g (83%) ofCompound 3 in the form of a yellow oil.

IR 1435, 1411, 1380, 1371, 1317, 1199, 1142, 1089, 1067, 854, 735, 697,700 cm-¹; ¹H NMR (400 MHz, CDCl₃) δ 7.34-7.25 (m, 5H), 4.57 (d, AB syst,J=11.5 Hz, 1H), 4.51 (d, AB syst, J=11.5 Hz, 1H), 3.46 (ddd, apparentdt, J=5.9 Hz and J=3.3 Hz, 1H), 1.21 (s, 6H), 1.20 (s, 6H), 0.99 (ddd,J=11.3 Hz, J=4.6 Hz and J=3.3 Hz, 1H), 0.73 (ddd, J=7.5 Hz, J=5.9 Hz andJ=4.6 Hz, 1H), 0.19 (ddd, J=11.3 Hz, J=7.5 Hz and J=3.3 Hz, 1H); ¹³C NMR(100 MHz, CDCl₃) δ 137.8 (s), 128.3 (d, 2C), 128.1 (d, 2C), 127.6 (d),83.0 (s, 2C), 73.1 (t), 58.1 (d), 24.64 (q, 2C), 24.59 (q, 2C), 11.7(t); EI-MS m/z (relative intensity) 183 (M-Bn⁺, 5), 174 (2), 145 (2),144 (3), 131 (2), 130 (8), 129 (4), 104 (3), 101 (3), 92 (11), 91 (100),85 (3), 84 (7), 83 (10), 79 (2), 69 (2), 67 (2), 65 (7), 59 (2), 57 (2),55 (5). HRMS calculated for C₁₆H₂₃BO₃Na (M+Na⁺): 297.16325. Found:297.16352.

Example 18 Synthesis of potassium((trans)-2-(benzyloxy)cyclopropyltrifluoroborate

Potassium difluoride (8.93 g, 114 mmol, 7.0 equivalents) then water (14mL) are added successively to a solution of dioxaborolane (Example 17,4.48 g, 16.3 mmol) in methanol (70 mL) at ambient temperature. Aftervigorous stirring for 3 hours at ambient temperature, the reactionmedium is concentrated under reduced pressure. 100 ml of acetonitrile isadded to the medium followed by evaporating to dryness. This operationis carried out several times until the water is completely removed. Thepasty residue is suspended in acetonitrile (50 mL) then filtered oncotton in order to remove the excess KHF₂. The filtrate is evaporatedunder reduced pressure in order to produce a solid which is washed withdiethyl ether. After filtration, 3.44 g (83%) of Compound 8 is obtainedin the form of a white solid.

IR 1440, 1364, 1299, 1210, 1090, 1035, 930, 909, 871, 794, 724, 693cm-¹; ¹H NMR (400 MHz, D₆-acetone) δ 7.37-7.30 (m, 4H), 7.28-7.23 (m,1H), 4.51 (s, 2H), 3.20 (ddd, J=5.3 Hz, J=3.5 Hz and J=2.3 Hz, 1H), 0.35(m, 1H), 0.25 (ddd, J=7.5 Hz, J=5.3 Hz and J=3.6 Hz, 1H), −0.16 (ddd,apparent m, 1H); ¹³C NMR (100 MHz, D₆-acetone) δ 140.3 (s), 128.4 (d,2C), 127.9 (d, 2C), 127.3 (d), 72.5 (t), 58.4 (d, J² _(13C-B)=3.3 Hz),8.6 (t, J² _(13C-B)=3.3 Hz), mp>172° C. (dec.).

Example 20 Synthesis of benzyl (2,2,2-tribromoethyl) ether

Benzyl bromide (8.41 mL, 70.7 mmol, 2.0 equivalents), tetrabutylammoniumiodide (653 mg, 1.77 mmol, 5 mol %) then 25 ml of an aqueous solution ofsoda (2.12 g, 53.0 mmol, 1.5 equivalents) are added to a solution of2,2,2-tribromoethanol (10.0 g, 35.3 mmol) in dichloromethane (25 mL) at0° C. After stirring for 3 hours at ambient temperature, the phases areseparated and the aqueous phase is extracted with dichloromethane. Thecombined organic phases are dried over magnesium sulphate, filtered thenevaporated to dryness under reduced pressure. The residue is purified bychromatography on silica gel (Eluent: petroleum ether/AcOEt: 98/2 to95/5) in order to produce 12.1 g (92%) of Compound 9 in the form of awhite solid with a low melting point.

IR 1453, 1401, 1348, 1111, 1077, 991, 973, 913, 755, 726, 696, 629, 602cm-¹; ¹H NMR (400 MHz, CDCl₃) δ 7.45-7.31 (m, 5H), 4.90 (s, 2H), 4.24(s, 2H); ¹³C NMR (100 MHz, CDCl₃) δ 136.9 (s), 128.6 (d, 2C), 128.2 (d),127.8 (d, 2C), 84.8 (t), 74.0 (t), 40.2 (s); EI-MS m/z (relativeintensity) 376 (0.3), 374 (0.8), 372 (0.8) and 372 (0.3) (M^(+)), 265(2), 263 (4) and 261 (2) (M-OBn⁺), 121 (7), 107 (2), 106 (2), 105 (4),92 (10), 91 (100), 90 (2), 89 (2), 79 (7), 78 (3), 77 (8), 65 (10), 63(2), 51 (5), 50 (2).

Example 21 Synthesis of (Z)-2-benzyloxy-1-bromoethylne

Lithium aluminium hydride (61.1 mg, 1.61 mmol, 0.6 equivalents) is addedto a suspension of anhydrous chromium tribromide (prepared by dryingunder vacuum at 90° C. a finely divided powder of hexahydrated chromiumtribromide) (948 mg, 3.22 mmol, 1.2 equivalents) and iron powder (599mg, 10.7 mmol, 4.0 equivalents) in THF (40 mL) at 0° C. After stirringfor 30 minutes at ambient temperature, 2,2,2-tribromoethyl ether(Example 20, 1.00 g, 2.68 mmol) is added in one portion. The reactionmedium is stirred for 2.5 hours before being filtered on a pad of silicagel then rinsed with diethyl ether. 200 ml of water is added to thefiltrate, the phases are separated and the aqueous phase is extractedwith diethyl ether. The combined organic phases are dried over magnesiumsulphate, filtered then evaporated to dryness under reduced pressure.The residue is purified by chromatography on silica gel (Eluent:petroleum ether/AcOEt: 96/4) in order to produce 487 mg (85%) ofCompound 10 in the form of a pale yellow oil.

¹H NMR (400 MHz, CDCl₃) δ 7.41-7.31 (m, 5H), 6.65 (d, J=4.2 Hz, 1H),5.16 (d, J=4.2 Hz, 1H), 4.97 (s, 2H); ¹³C NMR (100 MHz, CDCl₃) δ 147.0(d), 136.4 (s), 128.6 (d, 2C), 128.3 (d), 127.4 (d, 2C), 83.3 (d), 74.4(t)

Example 22 Synthesis of (cis)-1-(benzyloxy)-2-bromocyclopropane

Diethylzinc (4.51 mL, 1 M in hexane, 4.51 mmol, 2.0 equivalents) thenchloroiodomethane (677 μL, 9.01 mmol, 4.0 equivalents) are addeddropwise to a solution of vinyl ether (Example 21, 480 mg, 2.25 mmol) indichloromethane (15 mL) at 0° C. After stirring for 9 hours at ambienttemperature, an additional quantity of diethylzinc (4.51 mL, 1 M inhexane, 4.51 mmol, 2.0 equivalents) and chloroiodomethane (677 μL, 9.01mmol, 4.0 equivalents) are added and the reaction medium is stirred foran additional 15 hours. The medium is hydrolyzed by the addition, at 0°C., of a saturated aqueous solution of ammonium chloride (15 mL), thephases are separated and the aqueous phase is extracted withdichloromethane. The combined organic phases are dried over magnesiumsulphate, filtered then evaporated to dryness under reduced pressure.The residue is purified by chromatography on silica gel (Eluent:petroleum ether/AcOEt: 95/5 to 90/10) in order to produce the expectedcompound in the form of a pale yellow oil.

IR 1454, 1347, 1259, 1207, 1140, 1093, 1047, 1029, 973, 804, 780, 735,696 cm-¹; ¹H NMR (400 MHz, CDCl₃) δ 7.43-7.28 (m, 5H), 4.79 (d, AB syst,J=11.3 Hz, 1H), 4.59 (d, AB syst, J=11.3 Hz, 1H), 3.27 (ddd, apparentdt, J=7.3 Hz and J=4.8 Hz, 1H), 2.88 (ddd, apparent dt, J=8.3 Hz andJ=5.2 Hz, 1H), 1.30 (ddd, apparent q, J=7.8 Hz, 1H), 1.07 (ddd, J=7.8Hz, J=5.4 Hz and J=4.5 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 137.3 (s),128.4 (d, 2C), 128.1 (d, 2C), 127.9 (d), 72.9 (t), 53.7 (d), 20.5 (d),16.0 (t); EI-MS m/z (relative intensity) 147 (M-Br⁺, 2), 117 (4), 92(8), 91 (100), 89 (3), 77 (2), 65 (13), 63 (2), 51 (³).

Example 23 Synthesis of2-[(cis)-2-(benzyloxy)cyclopropyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

tert-Butyllithium (1.82 mL, 1.7 M in hexane, 3.09 mmol, 2.0 equivalents)is added dropwise to a solution of bromocyclopropane (Example 22, 351mg, 1.55 mmol) in diethyl ether (10 mL) at −78° C. After stirring for 30minutes at this temperature, pinacol isopropoxyborate (946 μL, 4.64mmol, 3.0 equivalents) is added dropwise and the reaction medium is leftto return slowly to ambient temperature over 2 hours. After stirring for30 minutes at this temperature, the medium is hydrolyzed by the additionof a saturated aqueous solution of ammonium chloride (20 mL). The phasesare separated and the aqueous phase is extracted with diethyl ether. Thecombined organic phases are dried over magnesium sulphate, filtered thenevaporated to dryness under reduced pressure. The residue is purified bychromatography on silica gel (Eluent: petroleum ether/AcOEt: 90/10) inorder to produce 254 mg (60%) of expected compound in the form of a paleyellow oil.

IR 1435, 1404, 1350, 1319, 1213, 1143, 1046, 1027, 951, 863, 851, 735,697, 670, 611 cm-¹; ¹H NMR (400 MHz, CDCl₃) δ 7.39-7.24 (m, 5H), 4.57(d, AB syst, J=11.7 Hz, 1H), 4.46 (d, AB syst, J=11.7 Hz, 1H), 3.60(ddd, J=6.8 Hz, J=6.1 Hz and J=3.6 Hz, 1H), 1.25 (s, 6H), 1.23 (s, 6H),1.05 (ddd, J=8.1 Hz, J=4.7 Hz and J=3.6 Hz, 1H), 0.84 (ddd, J=10.3 Hz,J=6.1 Hz and J=4.8 Hz, 1H), 0.05 (ddd, J=10.3 Hz, J=8.1 Hz and J=6.8 Hz,1H); ¹³C NMR (100 MHz, CDCl₃) δ 138.2 (s), 128.1 (d, 2C), 127.8 (d, 2C),127.4 (d), 83.1 (s, 2C), 72.9 (t), 58.2 (d), 24.8 (q, 2C), 24.7 (q, 2C),11.3 (t); EI-MS m/z (relative intensity) 183 (M-Bn⁺, 5), 174 (2), 144(3), 130 (8), 129 (5), 125 (4), 104 (3), 101 (3), 92 (11), 91 (100), 85(4), 84 (8), 83 (10), 81 (6), 79 (4), 65 (8), 57 (3), 55 (7). HRMScalculated for C₁₆H₂₃O₃BNa (M+Na⁺): 297.16325. Found: 297.16348.

Example 24 Synthesis of potassium((cis)-2-(benzyloxy)cyclopropyltrifluoroborate

Potassium difluoride (499 g, 6.38 mmol, 7.0 equivalents) then water (1.0mL) are added to a solution of dioxaborolane (Example 23, 250 mg, 0.912mmol) in methanol (5 mL) at ambient temperature. After vigorous stirringfor 3 hours at ambient temperature, the reaction medium is concentratedunder reduced pressure. 10 ml of acetonitrile is added to the mediumfollowed by evaporating to dryness. This operation is carried outseveral times until the water is completely removed. The pasty residueis suspended in acetonitrile (10 mL) then filtered on cotton in order toremove the excess KHF₂. The filtrate is evaporated under reducedpressure in order to produce a solid which is washed with diethyl ether.After filtration, 129 mg (56%) of compound is obtained in the form of awhite solid.

IR 1356, 1338, 1207, 1098, 1029, 1010, 951, 934, 922, 905, 851, 779,741, 698, 642 cm-¹; ¹H NMR (400 MHz, D₆-DMSO) δ 7.35-7.28 (m, 4H),7.26-7.21 (m, 1H), 4.59 (d, AB syst, J=11.6 Hz, 1H), 4.37 (d, AB syst,J=11.6 Hz, 1H), 3.16 (m, 1H), 0.28-0.19 (m, 2H), −0.65 (m, 1H); ¹³C NMR(100 MHz, D₆-DMSO) δ 140.7 (s), 128.8 (d, 2C), 128.7 (d, 2C), 127.7 (d),72.4 (t), 58.6 (d), 8.8 (t), mp=180° C.

Example 26 Suzuki-Miyaura couplings on potassium transcyclopropyltrifluoroborates bearing COOEt

(trans)-2-(4-Methoxy-phenyl)-cyclopropyl acetic acid ethyl ester

The potassium trifluoroborate reagent (Example 1, 2.5 g, 11.4 mmol) issolubilized in a mixture of toluene (62.5 ml) and water (6.25 ml).4-bromo-anisole (2.1 ml, 17 mmol), palladium acetate (51 mg, 0.23 mmol)and n-butyl-di-adamantylphosphine (122 mg, 0.34 mmol) are added.Nitrogen is bubbled through the medium for 10 minutes. Caesium carbonate(10 g, 30.7 mmol) is added and the mixture is heated under nitrogen at100° C. overnight. Water is added and the expected product is extracted3 times with ethyl acetate. The combined organic phases are dried overmagnesium sulphate, filtered and concentrated in order to produce 5.4 gof a brown solid. The expected product is purified by chromatography onsilica gel (heptane/ethyl acetate gradient). The expected product isobtained in the form of an orange solid (1.25 g, 5.7 mmol, yield 50%).¹H-NMR (CDCl₃, 300 MHz) δ 7.03 (d, J=8.6 Hz, 2H), 6.82 (d, J=8.7 Hz,2H), 4.16 (q, J=7.1 Hz, 2H), 3.78 (s, 3H), 2.47 (m, 1H), 1.81 (m, 1H),1.55 (m, 1H), 1.25 (m, 4H); LC/MS>99%, m/z (M+H)⁺=221.4.

All the other products are obtained following the same procedure.

(trans)-2-Pyrimidin-5-yl-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 9.08 (s, 1H), 8.52 (s, 1H), 4.19 (q, J=7.1 Hz,2H), 2.48 (m, 1H), 1.98 (m, 1H), 1.70 (m, 1H), 1.37 (m, 1H), 1.29 (t,J=7.1 Hz, 3H); LC/MS>99%, m/z (M+H)⁺=193.3.

(trans)-2-(6-Chloropyridin-3-yl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.21 (d, J=2.5 Hz, 1H), 7.32 (dd, J=2.5 Hz,J=8.2 Hz, 1H), 7.23 (d, J=8.2 Hz, 1H), 4.18 (q, J=7.1 Hz, 2H), 2.50 (m,1H), 1.90 (m, 1H), 1.65 (m, 1H), 1.28 (m, 4H); LC/MS>98%, m/z(M+H)⁺=226.3.

(trans)-2-(6-Trifluoromethyl-pyridin-3-yl)-cyclopropanecarboxylic acidethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.54 (d, J=1.8 Hz, 1H), 7.60 (d, J=8.1 Hz,1H), 7.50 (dd, J=1.8 Hz, J=8.1 Hz, 1H), 4.19 (q, J=7.1 Hz, 2H), 2.59 (m,1H), 1.98 (m, 1H), 1.73 (m, 1H), 1.37 (m, 1H), 1.29 (t, J=7.1 Hz, 3H);LC/MS>99%, m/z (M+H)⁺=260.2.

(trans)-2-(5-Cyano-pyridin-2-yl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.70 (dd, J=0.8 Hz, J=2.2 Hz, 1H), 7.82 (dd,J=2.2 Hz, J=8.1 Hz, 1H), 7.37 (dd, J=0.8 Hz, J=8.1 Hz, 1H), 4.17 (q,J=7.1 Hz, 2H), 2.61 (m, 1H), 2.33 (m, 1H), 1.68 (m, 2H), 1.28 (t, J=7.1Hz, 3H); LC/MS>98%, m/z (M+H)⁺=217.3.

(trans)-2-(3,4-Dimethoxyphenyl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 6.77 (d, J=8.7 Hz, 1H), 6.64 (m, 2H), 4.17 (q,J=7.1 Hz, 2H), 3.87 (s, 3H), 3.85 (s, 3H), 2.49 (m, 1H), 1.83 (m, 1H),1.55 (m, 1H), 1.28 (m, 4H); LC/MS>99%, m/z (M+H)⁺=251.3.

(trans)-2-(3-Trifluoromethyl-phenyl)-cyclopropanecarboxylic acid ethylester

¹H-NMR (CDCl₃, 300 MHz) δ 7.37 (m, 4H), 4.18 (q, J=7.1 Hz, 2H), 2.57 (m,1H), 1.93 (m, 1H), 1.65 (m, 1H), 1.34 (m, 1H), 1.28 (t, J=7.1 Hz, 3H);LC/MS>99%, m/z (M+H)⁺=259.3.

(trans)-2-(3-Methoxyphenyl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 7.19 (dd, J=7.9 Hz, 1H), 6.76 (ddd, J=8.2 Hz,J=2.6 Hz, J=0.9 Hz, 1H), 6.69 (m, 1H), 6.64 (dd, J=2.6 Hz, 1H), 4.17 (q,J=7.1 Hz, 2H), 3.79 (s, 3H), 2.49 (m, 1H), 1.90 (m, 1H), 1.59 (m, 1H),1.29 (m, 4H); LC/MS>99%, m/z (M+H)⁺=291.2.

(trans)-2-Quinolin-3-yl-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.75 (d, J=2.1 Hz, 1H), 8.06 (d, J=8.4 Hz,1H), 7.77 (d, J=2.1 Hz, 2H), 7.73 (d, J=8.4 Hz, 1H), 7.65 (ddd, J=7.7Hz, J=7.7 Hz, J=1.4 Hz, 1H), 7.51 (ddd, J=7.7 Hz, J=7.7 Hz, J=1.4 Hz,1H), 4.19 (t, J=7.1 Hz, 2H), 2.70 (m, 1H), 2.03 (m, 1H), 1.72 (m, 1H),1.45 (m, 1H), 1.30 (t, J=7.1 Hz, 3H); LC/MS>99%, m/z (M+H)⁺=242.3.

(trans)-2-Isoquinolin-4-yl-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 9.17 (bs, 1H), 8.33 (bs, 1H), 8.16 (d, J=8.4Hz, 1H), 8.0 (m, 1H), 7.79 (ddd, J=7.7 Hz, J=7.7 Hz, J=1.4 Hz, 1H), 7.66(ddd, J=7.7 Hz, J=7.7 Hz, J=1.4 Hz, 1H), 4.27 (q, J=7.1 Hz, 2H), 2.91(m, 1H), 197 (m, 1H), 1.73 (m, 1H), 1.48 (m, 1H), 1.34 (t, J=7.1 Hz,3H); LC/MS>99%, m/z (M+H)⁺=242.3.

(trans)-2-Isoquinolin-1-yl-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.75 (m, 2H), 7.82 (m, 1H), 7.66 (m, 2H), 7.49(d, J=5.7 Hz, 1H), 4.21 (q, J=7.2 Hz, 2H), 3.33 (m, 1H), 2.44 (m, 1H),1.82 (m, 1H), 1.73 (m, 1H), 1.30 (t, J=7.2 Hz, 3H); LC/MS>99%, m/z(M+H)⁺=242.3.

(trans)-2-(5-Fluoropyridin-3-yl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.31 (d, J=2.6 Hz, 1H), 8.27 (bt, 1H), 7.05(ddd, J=9.4 Hz, J=2.2 Hz, J=2.2 Hz, 1H), 4.17 (q, J=7.1 Hz, 2H), 2.52(m, 1H), 1.93 (m, 1H), 1.67 (m, 1H), 1.32 (m, 1H), 1.28 (t, J=1.7 Hz,3H); LC/MS>99%, m/z (M+H)⁺=210.3.

(trans)-2-Pyridin-3-yl-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.45 (m, 2H), 7.37 (ddd, J=7.9 Hz, J=3.4 Hz,J=3.4 Hz, 1H), 7.23 (d, J=7.9 Hz, 1H), 4.18 (q, J=7.1 Hz, 2H), 2.52 (m,1H), 1.93 (m, 1H), 1.65 (m, 1H), 1.32 (m, 1H), 1.29 (t, J=7.1 Hz, 3H);LC/MS>99%, m/z (M+H)⁺=192.2.

(trans)-2-(2-Fluorophenyl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 7.18 (m, 1H), 7.00 (m, 3H), 4.18 (q, J=7.0 Hz,2H), 2.66 (m, 1H), 1.94 (m, 1H), 1.60 (m, 1H), 1.35 (m, 1H), 1.29 (t,J=7.0 Hz, 3H); LC/MS>99%, m/z (M+H)⁺=209.3.

(trans)-2-(6-Fluoropyridin-3-yl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.01 (m, 1H), 7.44 (ddd, J=8.9 Hz, J=2.5 Hz,J=2.5 Hz, 1H), 6.83 (dd, J=8.9 Hz, J=2.5 Hz, 1H), 4.16 (q, J=7.1 Hz,2H), 2.45 (m, 1H), 1.86 (m, 1H), 1.61 (m, 1H), 1.26 (m, 4H); LC/MS>99%,m/z (M+H)⁺=210.3.

(trans)-2-Thiophen-3-yl-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 7.26 (dd, J=5.0 Hz, J=3.0 Hz, 1H), 6.97 (m,1H), 6.84 (dd, J=5.0 Hz, J=3.0 Hz, 1H), 4.17 (q, J=7.1 Hz, 2H), 2.55 (m,1H), 1.87 (m, 1H), 1.57 (m, 1H), 1.29 (m, 4H); LC/MS>99%, m/z(M+H)⁺=197.1.

(trans)-2-(5-Formyl-furan-2-yl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 9.49 (s, 1H), 7.16 (d, J=3.6 Hz, 1H), 6.32 (d,J=3.6 Hz, 1H), 4.17 (q, J=7.2 Hz, 2H), 2.58 (m, 1H), 2.18 (m, 1H), 1.59(m, 2H), 1.28 (t, J=7.2 Hz, 3H); LC/MS>99%, m/z (M+H)⁺=209.2.

(trans)-2-(2,2-Difluoro-benzo[1,3]dioxol-5-yl)-cyclopropanecarboxylicacid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 6.95 (d, J=8.3 Hz, 1H), 6.80 (dd, J=8.3 Hz,J=1.7 Hz, 1H), 6.84 (d, J=1.7 Hz, 1H), 4.17 (q, J=7.1 Hz, 2H), 2.51 (m,1H), 1.84 (m, 1H), 1.60 (m, 1H), 1.27 (m, 4H); LC/MS>99%, m/z(M+H)⁺=271.2.

(trans)-2-Benzo[1,3]dioxol-5-yl-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 6.71 (d, J=7.98 Hz, 1H), 6.60 (ddd, J=7.9 Hz,J=1.8 Hz, J=0.42 Hz, 1H), 6.56 (d, J=1.8 Hz, 1H), 4.16 (q, J=7.1 Hz,2H), 2.45 (m, 1H), 1.80 (m, 1H), 1.53 (m, 1H), 1.24 (m, 4H); LC/MS>99%,m/z

(trans)-2-(6-Methylpyridin-3-yl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.34 (d, J=2.3 Hz, 1H), 7.25 (dd, J=8.2 Hz,J=2.3 Hz, 1H), 7.07 (d, J=8.2 Hz, 1H), 4.17 (q, J=7.1 Hz, 2H), 2.50 (m,1H), 1.89 (m, 1H), 1.62 (m, 1H), 1.30 (m, 4H); LC/MS>99%, m/z(M+H)⁺=206.3

(trans)-2-(5-Fluoropyridin-2-yl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.30 (d, J=2.7 Hz, 1H), 7.27 (m, 2H), 4.17 (q,J=7.1 Hz, 2H), 2.58 (m, 1H), 2.2 (m, 1H), 1.60 (m, 1H), 1.28 (m, 4H);LC/MS>99%, m/z (M+H)⁺=210.3

(trans)-2-(5-Trifluoromethyl-pyridin-2-yl)-cyclopropanecarboxylic acidethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.68 (s, 1H), 7.78 (dd, J=8.2 Hz, J=1.8 Hz,1H), 7.35 (d, J=8.2 Hz, 1H), 4.16 (q, J=7.2 Hz, 2H), 2.62 (m, 1H), 2.30(m, 1H), 1.65 (m, 2H), 1.27 (t, J=7.2 Hz, 3H); LC/MS>99%, m/z(M+H)⁺=260.3

(trans)-2-(4-Methylpyridin-2-yl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.31 (d, J=5.0 Hz, 1H), 7.07 (d, J=0.7 Hz,1H), 6.93 (dd, J=5.0 Hz, J=0.7 Hz, 1H), 4.18 (q, J=7.2 Hz, 2H), 2.55 (m,1H), 2.23 (m, 1H), 1.6 (m, 2H), 1.29 (t, 7.2 Hz, 3H); LC/MS>99%, m/z(M+H)⁺=206.3

(trans)-2-(2-Fluoropyridin-4-yl)-cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.11 (d, J=5.3 Hz, 1H), 6.89 (dt, J=5.3 Hz,J=1.6 Hz, 1H), 6.64 (s, 1H), 4.19 (q, J=7.1 Hz, 2H), 2.52 (m, 1H), 2.02(m, 1H), 1.72 (m, 1H), 1.39 (m, 1H), 1.35 (t, J=7.1 Hz, 3H); LC/MS>99%,m/z (M+H)⁺=210.3

(trans)-2-(2,3-Dihydro-benzofuran-4-yl)-cyclopropanecarboxylic acidethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 7.04 (dd, J=7.8 Hz, 1H), 6.65 (d, J=7.1 Hz,1H), 6.40 (d, J=7.8 Hz, 1H), 4.60 (t, J=8.7 Hz, 2H), 4.18 (q, 7.1 Hz,2H), 3.24 (d, J=7.8 Hz, 2H), 2.42 (m, 1H), 1.90 (m, 1H), 1.58 (m, 1H),1.30 (m, 4H).

Ethyl-(trans)-2-[(Z)-3-ethoxy-3-oxo-prop-1-enyl]cyclopropanecarboxylate

¹H-NMR (CDCl₃, 300 MHz) δ 5.77 (dm, J=11.4 Hz, 1H), 5.44 (dd, J=11.4 Hz,J=10.8 Hz, 1H), 4.19 (q, J=7.0 Hz, 2H), 4.13 (q, J=7.0 Hz, 2H), 3.40 (m,1H), 1.74 (m, 1H), 1.59 (m, 1H), 1.29 (t, J=7.0 Hz, 3H), 1.26 (t, J=7.0Hz, 3H), 1.03 (m, 1H).

Ethyl-(trans)-2-[(E)-cinnamyl]cyclopropanecarboxylate

¹H-NMR (CDCl₃, 300 MHz) δ 7.4-7.12 (m, 5H), 6.40 (d, J=15.9 Hz, 1H),6.17 (dt, J=15.9 Hz, J=6.9 Hz, 1H), 4.09 (q, J=7.0 Hz, 2H), 2.21 (m,2H), 1.43 (m, 2H), 1.23 (t, J=7.0 Hz, 3H), 1.20 (m, 1H), 0.77 (m, 1H).

Example 27 Suzuki-Miyaura couplings on potassium transcyclopropyltrifluoroborates bearing —CH₂—NHZ

The following products are obtained according to the procedure presentedin Example 26, starting from the potassium trifluoroborate reagentdescribed in Example 9.

((trans)-2-Pyrimidin-5-yl-cyclopropylmethyl)-carbamic acid benzyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 9.04 (s, 1H); 8.46 (s, 2H); 7.35 (m, 5H); 5.13(s, 2H); 5.02 (bs, 1H); 3.29 (m, 2H); 1.87 (m, 1H); 1.42 (m, 1H); 1.08(m, 2H).

[(trans)-2-(4-Methoxy-phenyl)-cyclopropylmethyl]-carbamic acid benzylester

¹H-NMR (CDCl₃, 300 MHz) δ 7.34 (m, 5H); 6.97 (d, J=8.5 Hz, 2H); 6.80 (d,J=8.5 Hz, 2H); 5.11 (s, 2H); 4.93 (bs, 1H); 3.78 (s 3H); 3.22 (m, 2H);1.77 (m, 1H); 1.24 (m, 1H); 0.87 (m, 2H).

(trans)-2-(3-Methoxy-phenyl)-cyclopropylmethyl]-carbamic acid benzylester

¹H-NMR (CDCl₃, 300 MHz) δ 7.37 (m, 5H); 7.18 (dd, J=7.9 Hz, J=7.9 Hz,1H); 6.72 (dd, J=2.5 Hz, J=8.2 Hz, 1H); 6.65 (d, J=8.2 Hz, 1H); 6.60 (m,1H); 5.12 (s, 2H; 4.92 (s, 1H); 3.80 (s, 3H); 3.25 (m, 2H; 1.80 (m, 1H);1.34 (m, 1H; 0.95 (m, 2H).

[(trans)-2-(2-Fluoro-phenyl)-cyclopropylmethyl]-carbamic acid benzylester

¹H-NMR (CDCl₃, 300 MHz) δ 7.36 (m, 5H); 7.16 (m, 1H); 7.03 (m, 2H); 6.92(dd, J=7.0 Hz, J=7.0 Hz, 1H); 5.13 (s, 2H); 5.01 (bs, 1H); 3.43 (m, 1H);3.14 (m, 1H); 1.98 (m, 1H); 1.31 (m, 1H); 0.98 (m, 2H).

[(trans)-2-(5-Fluoro-pyridin-3-yl)-cyclopropylmethyl]-carbamic acidbenzyl ester*

¹H-NMR (CDCl₃, 300 MHz) δ 8.25 (d, J=2.6 Hz, 1H); 8.21 (s, 1H); 7.34 (m,5H); 6.96 (d, J=9.4 Hz, 1H); 5.11 (s, 2H); 5.00 (bs, 1H); 3.25 (m, 2H);1.87 (m, 1H); 1.35 (m, 1H); 1.00 (m, 2H).

((trans)-2-Pyridin-3-yl-cyclopropylmethyl)-carbamic acid benzyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 8.40 (m, 2H); 7.34 (m, 6H); 7.21 (m, 1H); 5.10(s, 2H); 4.96 (bs, 1H); 3.26 (m, 2H); 1.85 (m, 1H); 1.34 (m, 1H); 1.00(m, 2H).

[(trans)-2-(2-Acetyl-phenyl)-cyclopropylmethyl]-carbamic acid benzylester

¹H-NMR (CDCl₃, 300 MHz) δ 7.68 (dd, J=1.2 Hz, J=7.6 Hz, 1H); 7.34 (m,7H); 7.08 (d, J=7.6 Hz, 1H); 5.13 (s, 2H); 3.79 (m, 1H); 2.76 (m, 1H);2.63 (s, 3H); 2.26 (m, 1H); 1.10 (m, 2H); 0.85 (m, 1H).

((trans)-2-Isoquinolin-1-yl-cyclopropylmethyl)-carbamic acid benzylester

¹H-NMR (CDCl₃, 300 MHz) δ 8.39 (d, J=8.3 Hz, 1H); 8.35 (d, J=5.7 Hz,1H); 7.82 (d, J=7.5 Hz, 1H); 7.65 (m, 2H); 7.46 (dd, J=0.6 Hz; J=5.7 Hz,1H); 7.34 (m, 5H); 5.13 (s, 2H); 5.01 (bs, 1H); 3.43 (m, 2H); 2.75 (m,1H); 1.84 (m, 1H); 1.55 (m, 1H); 1.12 (m, 1H).

((trans)-2-Thiophen-3-yl-cyclopropylmethyl)-carbamic acid benzyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 7.34 (m, 5H); 7.21 (dd, J=3.0 Hz, J=4.9 Hz,1H); 6.85 (s, 1H); 6.78 (d, J=4.9 Hz, 1H); 5.11 (s, 2H); 4.90 (bs, 1H);3.22 (m, 2H); 1.85 (m, 1H); 1.28 (m, 1H); 0.87 (m, 2H).

Example 28 Suzuki-Miyaura couplings on potassium transcyclopropyltrifluoroborates bearing —OBn

Suzuki-Miyaura coupling between compound 8 and iodobenzene:

Palladium diacetate (1.3 mg, 5.9 μmol, 3 mol %), XantPhos (6.8 mg, 12μmol, 6 mol %), caesium carbonate (192 mg, 0.590 mmol, 3.0 equivalents),potassium cyclopropyltrifluoroborate 8 (50.0 mg, 0.197 mmol),tert-butanol (1.0 mL), water (50 μL) and finally iodobenzene (33 μL,0.30 mmol, 1.5 equivalents) are successively added into a sealed tube,under an inert atmosphere. The tube is then closed (Teflon stopper) thenimmersed in an oil bath pre-heated to 120° C. After stirring for 24hours at this temperature, the reaction medium is cooled down to ambienttemperature then filtered on a celite pad (rinsing with AcOEt) andevaporated to dryness under reduced pressure. Purification bychromatography on silica gel (Eluent: petroleum ether/AcOEt: 95/5)produces a mixture of Compound 14 and enol ether 15 in a ratio of 77/23.The separation of this mixture can be obtained by preparative TLC on asilica plate (Eluent: petroleum ether/AcOEt: 95/5) in order to produce22.5 mg (51%) of Compound 14 in the form of a colourless oil.

Suzuki-Miyaura coupling between Compound 8 and bromobenzene:

Palladium diacetate (1.3 mg, 5.9 μmol, 3 mol %), XantPhos (6.8 mg, 12μmol, 6 mol %), caesium carbonate (192 mg, 0.590 mmol, 3.0 equivalents),potassium cyclopropyltrifluoroborate 8 (50.0 mg, 0.197 mmol),tert-butanol (1.0 mL), water (50 μL) and finally bromobenzene (31.1 μL,0.295 mmol, 1.5 equivalents) are successively added into a sealed tube,under an inert atmosphere. The tube is then closed (Teflon stopper) thenimmersed in an oil bath pre-heated to 120° C. After stirring for 24hours at this temperature, the reaction medium is cooled down to ambienttemperature then filtered on a celite pad (rinsing with AcOEt) andevaporated to dryness under reduced pressure. Purification bychromatography on silica gel (Eluent: petroleum ether/AcOEt: 95/5)produces a mixture of cyclopropene 14 and enol ether 15 in a ratio of50/50. Separation of this mixture can be obtained by preparative TLC ona silica plate (Eluent: petroleum ether/AcOEt: 95/5) in order to produce16.4 mg (37%) of Compound 14 in the form of a colourless oil.

[(1R*,2S*)-2-(Benzyloxy)cyclopropyl]benzene (14)

IR 1604, 1496, 1454, 1366, 1260, 1208, 1146, 1092, 1071, 1024, 910, 870,735, 695, 613 cm⁻¹; ¹H NMR (400 MHz, CDCl₃) δ 7.35-7.22 (m, 7H),7.18-7.13 (m, 1H), 7.01-6.98 (m, 2H), 4.63 (d, AB syst, J=11.7 Hz, 1H),4.60 (d, AB syst, J=11.7 Hz, 1H), 3.44 (ddd, J=6.5 Hz, J=3.6 Hz andJ=2.6 Hz, 1H), 2.15 (ddd, J=10.2 Hz, J=6.4 Hz and J=2.6 Hz, 1H), 1.34(ddd, J=10.2 Hz, J=6.1 Hz and J=3.6 Hz, 1H), 1.05 (ddd, apparent q,J=6.4 Hz, 1H); ¹³C NMR (100 MHz, CDCl₃) δ 141.1 (s), 137.8 (s), 128.4(d, 2C), 128.3 (d, 2C), 128.0 (d, 2C), 127.8 (d), 125.9 (d, 2C), 125.7(d), 73.0 (t), 61.7 (d), 23.9 (d), 16.0 (t); EI-MS m/z (relativeintensity) 224 (Mt^(+), 0.1), 181 (3), 180 (21), 133 (M-Bn⁺, 17), 115(3), 106 (9), 105 (100), 104 (7), 103 (10), 92 (10), 91 (87), 89 (3), 79(15), 78 (6), 77 (15), 65 (17), 63 (4), 51 (7). HRMS calculated forC₁₆H₁₆ONa (M+Na⁺): 247.10934. Found: 247.10901.

[3-(Benzyloxy)prop-2-en-1-yl]benzene (15)

¹H NMR (400 MHz, CDCl₃) (Z)-isomer δ 7.39-7.14 (m, 10H), 6.14 (dt, J=6.2Hz and J=1.2 Hz, 1H), 4.84 (s, 2H), 4.62 (td, J=7.5 Hz and J=6.2 Hz, 1H,H₂), 3.48 (br d, J=7.5 Hz, 2H, H₇); (E)-isomer δ 7.39-7.14 (m, 10H,H_(Ar)), 6.44 (dt, J=12.6 Hz and J=1.2 Hz, 1H, H₃), 5.04 (dt, J=12.6 Hzand J=7.4 Hz, 1H, H₂), 4.74 (s, 2H, H₄), 3.27 (br d, J=7.1 Hz, 2H, H₇);¹³C NMR (100 MHz, CDCl₃) (Z)-isomer δ 145.1 (d, C₃), 141.6 (s, C₅ orC₉), 137.6 (s, C₉ or C₅), 128.5 (d), 128.4 (d) and 128.3 (d) (6 C_(Ar)),127.6 (d, 2C, C_(Ar)), 125.7 (d, 2C, C_(Ar)), 106.4 (d, C₂), 73.7 (t,C₄), 30.3 (t, C₇); (E)-isomer δ 146.9 (d, C₃), 141.5 (s, C₅ or C₉),137.1 (s, C₉ or C₅), 128.5 (d), 128.4 (d), 128.3 (d) (6 C_(Ar)), 127.9(d, 2C, C_(Ar)), 125.9 (d, 2C, C_(Ar)), 103.8 (d, C₂), 71.1 (t, C₄),34.1 (t, C₇).

Example 29 Suzuki-Miyaura couplings on potassium ciscyclopropyltrifluoroborates bearing COOEt

(cis)-2-(4-chlorophenyl)cyclopropyl acetic acid ethyl ester

4-Bromochlorobenzene (8.7 g, 45.5 mmol),palladium-diphenylphosphinoferrocene (832 mg, 1.14 mmol) and caesiumcarbonate (22.2 g, 68.2 mmol) are added successively to a solution ofpotassium cis trifluoroborate (5.0 g, 22.7 mmol) in a mixture of THF (20ml) and water (20 ml). The reaction medium purged with nitrogen isheated at 100° C. for 48 hours. The insoluble part is filtered onClarcel®, then washed with water and ethyl acetate. The phases areseparated and the aqueous phase is extracted 3 times with ethyl acetate.The organic phases are dried over magnesium sulphate, filtered,concentrated to dryness in order to produce 5.55 g of a brown oil.Purification by chromatography on silica gel (Eluent: Heptane/AcOEtgradient) produces the expected compound in the form of a brown oil.

¹H-NMR (CDCl₃, 300 MHz) δ 7.23 (m, 4H), 3.92 (q, J=7.5 Hz, 2H), 2.54 (q,J=9.0 Hz, 1H), 2.10 (m, 1H), 1.69 (m, 1H), 1.33 (m, 1H), 1.04 (t, J=7.5Hz, 3H)

All the other products are obtained following the same procedure.

(cis)-2-(3-trifluoromethylphenyl)cyclopropanecarboxylic acid ethyl ester

¹H-NMR (CDCl₃, 300 MHz) δ 7.38 (m, 4H), 3.81 (qd, J₁=7.3 Hz, J₂=1.1 Hz,2H), 2.53 (q, J=8.4 Hz, 1H), 2.06 (m, 1H), 1.66 (m, 1H), 1.32 (m, 1H),0.91 (t, J=7.3 Hz, 3H); LC/MS>90%, m/z (M+H)⁺=259.3

(cis)-2-(1,3-benzodioxol-5-yl)cyclopropanecarboxylic acid ethyl ester

¹H-NMR (acetone-d6, 300 MHz) δ 6.65 (m, 3H), 5.84 (s, 2H), 3.78 (q,J=6.8 Hz, 2H), 2.45 (q, J=8.2 Hz, 1H), 1.45 (m, 1H), 1.21 (m, 1H), 0.92(t, J=6.8 Hz, 3H); LC/MS>98%, m/z (M+H)⁺=235.3

(cis)-2-(6-Trifluoromethyl-pyridin-3-yl)cyclopropanecarboxylic acidethyl ester

¹H-NMR (acetone-d6, 300 MHz) δ 8.54 (s, 1H), 7.8 (dm, J=9.4 Hz, 1H),7.62 (d, J=9.4 Hz, 1H), 3.75 (m, 2H), 2.64 (q, J=8.6 Hz, 1H), 2.14 (m,1H), 1.62 (m, 1H), 1.41 (m, 1H), 0.86 (t, J=7.7 Hz, 3H); LC/MS>96%, m/z(M+H)⁺=260.3

Example 30 Suzuki-Miyaura couplings on potassium ciscyclopropyltrifluoroborates bearing —OBn

Suzuki-Miyaura coupling between Compound 13 and iodobenzene:

Palladium diacetate (1.3 mg, 5.9 μmol, 3 mol %), XantPhos (6.8 mg, 12μmol, 6 mol %), caesium carbonate (192 mg, 0.590 mmol, 3.0 equivalents),potassium cyclopropyltrifluoroborate 13 (50.0 mg, 0.197 mmol),tert-Butanol (1.0 mL), water (50 μL) and finally iodobenzene (33 μL,0.30 mmol, 1.5 equivalents) are successively added, under an inertatmosphere, into a sealed tube. The tube is then closed (Teflon stopper)then immersed in an oil bath pre-heated to 120° C. After stirring for 24hours at this temperature, the reaction medium is cooled down to ambienttemperature then filtered on a celite pad (rinsing with AcOEt) andevaporated to dryness under reduced pressure. Purification bychromatography on silica gel (Eluent: petroleum ether/AcOEt: 97/3 then96/4) produces 42.0 mg (95%) of Compound 16 in the form of a colourlessoil.

Suzuki-Miyaura coupling between Compound 13 and bromobenzene:

Palladium diacetate (1.3 mg, 5.9 μmol, 3 mol %), XantPhos (6.8 mg, 12μmol, 6 mol %), caesium carbonate (192 mg, 0.590 mmol, 3.0 equivalents),potassium cyclopropyltrifluoroborate 13 (50.0 mg, 0.197 mmol),tert-Butanol (1.0 mL), water (50 μL) and finally bromobenzene (31.1 μL,0.295 mmol, 1.5 equivalents) are successively added, under an inertatmosphere, into a sealed tube. The tube is then closed (Teflon stopper)then immersed in an oil bath pre-heated to 120° C. After stirring for 24hours at this temperature, the reaction medium is cooled down to ambienttemperature then filtered on a celite pad (rinsing with AcOEt) andevaporated to dryness under reduced pressure. Purification bychromatography on silica gel (Eluent: petroleum ether/AcOEt: 97/3 then96/4) produces 43.3 mg (98%) of Compound 16 in the form of a colourlessoil.

[(1R*,2R*)-2-(Benzyloxy)cyclopropyl]benzene

IR 1603, 1497, 1454, 1345, 1222, 1182, 1083, 1047, 1027, 938, 766, 733,694, 642 cm-¹; ¹H NMR (400 MHz, CDCl₃) δ 7.32-7.18 (m, 8H, H_(Ar)),7.10-7.07 (m, 2H, H₁₀), 4.27 (d, AB syst, J=11.2 Hz, 1H, H₄), 4.16 (d,AB syst, J=11.2 Hz, 1H, H_(4′)), 3.59 (ddd, apparent td, J=6.4 Hz andJ=3.9 Hz, 1H, H₃), 2.02 (ddd, J=9.5 Hz, J=7.2 Hz and J=6.3 Hz, 1H, H₂),1.23-1.14 (m, 2H, H₁); ¹³C NMR (100 MHz, CDCl₃) δ 137.7 (s, C₅ or C₉),137.5 (s, C₉ or C₅), 128.21 (d, 2C), 128.16 (d, 2C), 127.93 (d, 2C),127.88 (d, 2C) (8 C_(Ar)), 127.6 (d, C₈), 125.6 (d, C₁₀), 72.7 (t, C₄),58.4 (d, C₃), 22.8 (d, C₂), 12.9 (t, CO; EI-MS m/z (relative intensity)224 (M^(+), 0.1), 181 (4), 180 (23), 133 (M-Bn⁺, 16), 115 (3), 106 (9),105 (100), 104 (7), 103 (11), 92 (10), 91 (85), 89 (3), 79 (15), 78 (6),77 (16), 65 (17), 63 (4), 51 (7). HRMS calculated for C₁₆H₁₆ONa (M+Na⁺):247.10934. Found: 247.10930.

Example 31 Synthesis of (+/−)-tasimelteon

Route 1:

4-bromo-2,3-dihydrobenzofurane (1 g, 5.03 mmol), palladium diacetate (23mg, 0.10 mmol) and n-butyldi-adamantylphosphine (54 mg, 0.15 mmol) areadded successively to a solution of potassium trifluoroborate (Example1, 2.21 g, 10.05 mmol) in a mixture of toluene (55 ml) and water (5.5ml). The medium is purged with nitrogen for 10 minutes. Caesiumcarbonate (4.4 g, 13.56 mmol) is added and the reaction mixture isheated at 100° C. overnight. After hydrolysis with water, the aqueousphase is extracted 3 times with ethyl acetate. The combined organicphases are dried over magnesium sulphate, filtered and concentrated todryness in order to produce 1.4 g of a brown oil. Purification bychromatography on silica gel (heptane/ethyl acetate gradient) produces910 mg (78%) of expected compound in the form of a yellow oil.

¹H-NMR (CDCl₃, 300 MHz) δ 7.04 (dd, J=7.8 Hz, 1H), 6.65 (d, J=8.1 Hz,1H), 6.40 (d, J=7.8 Hz, 1H), 4.60 (t, J=8.7 Hz, 2H), 4.18 (q, 7.1 Hz,2H), 3.24 (t, J=8.7 Hz, 2H), 2.42 (m, 1H), 1.90 (m, 1H), 1.58 (m, 1H),1.30 (m, 4H). ¹³C-NMR (CDCl₃, 300 MHz): 174.0, 160.2, 137.1, 128.7,127.0, 116.5, 107.9, 71.5, 61.2, 29.0, 24.4, 23.3, 16.6, 14.7 LCUV>99%.

A solution of ethyl ester (800 mg, 3.4 mmol) in a 2 N aqueous sodamixture (8.6 ml, 17.3 mmol) and ethanol (4 ml) is heated at 50° C. for 2h. 1 N hydrochloric acid is then added, then the aqueous phase isextracted 3 times with ethyl acetate. The combined organic phases arewashed with water then with salt water, dried over magnesium sulphate,filtered and concentrated to dryness in order to produce 680 mg of abeige solid (98%).

mp=146° C.

¹H-NMR (CDCl₃, 300 MHz) δ 7.04 (dd, J=7.8 Hz, 1H), 6.65 (d, J=7.8 Hz,1H), 6.41 (d, J=7.8 Hz, 1H), 4.60 (t, J=8.7 Hz, 2H), 3.25 (t, J=8.7 Hz,2H), 2.49 (m, 1H), 1.89 (m, 1H), 1.62 (m, 1H), 1.40 (m, 1H).

¹³C-NMR (CDCl₃, 300 MHz) 180.1, 160.3, 136.5, 128.8, 127.1, 116.8,108.2, 77.5, 29.0, 25.3, 23.0, 17.0

LC/MS>99%, m/z [M+H]⁺=205.2.

Dimethylformamide (100 μl) and thionyl chloride (500 μl, 6.8 mmol) areadded to a solution of carboxylic acid (680 mg, 3.3 mmol) in 6.8 ml ofdichloromethane at ambient temperature. After 2 hours, the reactionmixture is concentrated to dryness, then taken up in 3.4 ml ofdichloromethane. The medium is cooled down to 0° C. in an ice/waterbath, then ammonia (13.6 ml) is added slowly. The observed suspension isstirred overnight at ambient temperature. Isopropyl ether is added, thesolid is filtered then washed two times with isopropyl ether in order toproduce 565 mg (83%) of expected compound in the form of a white solid.

mp=194° C.

¹H-NMR (CDCl₃, 300 MHz) δ 7.05 (dd, J=7.8 Hz, 1H), 6.68 (d, J=7.8 Hz,1H), 6.38 (d, J=7.8 Hz, 1H), 5.72 (s, 1H), 5.58 (s, 1H), 4.60 (t, J=8.7Hz, 2H), 3.26 (m, 2H), 2.44 (m, 1H), 1.83 (m, 1H), 1.63 (m, 1H), 1.30(m, 1H). ¹³C-NMR (CDCl₃, 300 MHz) 174.9, 160.2, 137.5, 128.7, 127.0,115.9, 107.9, 77.6, 29.0, 25.0, 23.8, 16.2

LC/MS>99%, m/z [M+H]⁺=204.2.

The amide (300 mg, 1.48 mmol) is added by portions to a suspension ofLAH (196 mg, 5.17 mmol) in tetrahydrofuran (3 ml) at ambient temperatureand under an inert atmosphere, then the medium is heated at reflux for 3hours and at ambient temperature overnight. Water (200 μl), 6 N aqueoussoda (200 μl), then again water (6000 are added to the medium at 0° C.The suspension obtained is filtered on celite and the filtrate isevaporated to dryness. The yellow oil obtained is taken up in 6 ml oftetrahydrofuran, then triethylamine (1 ml, 7.38 mmol) is added to themixture. Propionyl chloride (410 mg, 4.43 mmol) is added dropwise to themixture cooled down to 0° C. The medium is stirred for 1 h at 0° C. thenfor 2 h at ambient temperature. Water and dichloromethane are added,then the phases are separated. The aqueous phase is extracted 3 timeswith dichloromethane. The combined organic phases are washed with water,with salt water, then dried over magnesium sulphate, filtered andconcentrated to dryness in order to produce a yellow oil purified bychromatography on silica gel (heptane/ethyl acetate gradient). Theexpected product is obtained in the form of a yellow oil.

¹H-NMR (CDCl₃, 300 MHz) δ 7.04 (dd, J=7.8 Hz, 1H), 6.63 (d, J=7.8 Hz,1H), 6.35 (d, J=7.8 Hz, 1H), 5.64 (s, 1H), 4.61 (t, J=8.7 Hz, 2H), 3.29(m, 4H), 2.24 (q, J=7.5 Hz, 2H), 1.75 (m, 1H), 1.25 (m, 1H), 1.17 (t,J=7.5 Hz, 3H), 0.96 (m, 2H).

¹³C-NMR (CDCl₃, 300 MHz) 174.2, 160.0, 139.3, 128.6, 126.4, 116.0,107.2, 71.5, 44.0, 30.2, 29.0, 22.1, 20.1, 13.9, 10.3.

LC/MS>97%, m/z [M+H]⁺=246.2.

Route 2:

Sodium carbonate (373 mg, 3.52 mmol) is added to a solution of potassiumtrifluoroborate (Example 9, 730 mg, 2.35 mmol) in an acetonitrile (23.4ml)/water (11.7 ml) mixture. The medium is stirred for 1 h at ambienttemperature. A saturated aqueous solution of ammonium chloride is addeduntil a pH close to 6 is obtained then the medium is extracted 4 timeswith isopropyl ether. The organic phases are washed with water thendried over magnesium sulphate, filtered and concentrated to dryness inorder to produce a white solid (530 mg, yield 91%).

¹H-NMR (MeOD, 300 MHz) δ 7.33 (m, 5H), 5.06 (s, 2H), 3.02 (m, 2H), 1.12(m, 1H), 0.63 (m, 1H), 0.48 (m, 1H), −0.17 (m, 1H).

Boronic acid (530 mg, 2.13 mmol) is solubilized in a mixture of toluene(10.6 ml) and water (2.6 ml). Brominated dihydrobenzofuran (848 mg, 4.26mmol) and palladium-tetrakis (123 mg, 0.11 mmol) are added. The mediumis stirred whilst under vacuum, then under nitrogen 3 times. Potassiumphosphate (1.4 g, 6.39 mmol) is added, then the medium is heated at 100°C. overnight under nitrogen. Water is added and the expected product isextracted 3 times with ethyl acetate. The combined organic phases arewashed with water then with salt water, and they are dried overmagnesium sulphate, filtered and concentrated in order to produce 1.2 gof a brown oil. The expected product is purified by chromatography onsilica gel (heptane/ethyl acetate gradient) and it is obtained in theform of a yellow oil (413 mg, yield 60%). ¹H-NMR (CDCl3, 300 MHz) δ 7.29(m, 5H), 6.94 (dd, J=8.1 Hz, 1H), 6.54 (d, J=7.8 Hz, 1H), 6.26 (d, J=7.8Hz, 1H), 5.08 (s, 2H), 4.85 (s, 1H), 4.48 (t, J=8.7 Hz, 2H), 3.16 (m,4H), 1.66 (m, 1H), 1.23 (m, 1H), 0.90 (m, 1H), 0.81 (m, 1H).

¹³C-NMR (CDCl₃, 300 MHz) 160.0, 156.8, 139.2, 136.9, 129.0, 128.6,126.5, 116.2, 107.2, 71.4, 67.1, 45.6, 29.0, 22.5, 19.9, 13.5.

Palladium on carbon (38 mg) is added to a solution of carbamate (380 mg,1.17 mmol) in methanol (7.6 ml), degassed 3 times by vacuum/nitrogenpurges. The medium is again purged 3 times with nitrogen then placedunder a hydrogen atmosphere. The mixture is heated at 50° C. overnightunder hydrogen. The suspension obtained is filtered on celite then thefiltrate is evaporated to dryness. The yellow oil obtained is taken upin 5 ml of tetrahydrofuran, then triethylamine (819 μl, 5.85 mmol) isadded to the mixture. Propionyl chloride (308 μl, 3.51 mmol) is addeddropwise to the mixture cooled down to 0° C. The medium is stirred for 1h at 0° C. then for 1 h 30 at ambient temperature. Water anddichloromethane are added, then the phases are separated. The aqueousphase is extracted 3 times with dichloromethane. The combined organicphases are washed with water, with salt water, then dried over magnesiumsulphate, filtered and concentrated to dryness in order to produce ayellow oil purified by chromatography on silica gel (heptane/ethylacetate gradient). The expected product is obtained in the form of ayellow oil.

¹H-NMR (CDCl₃, 300 MHz) δ 7.04 (dd, J=7.8 Hz, 1H), 6.63 (d, J=7.8 Hz,1H), 6.35 (d, J=7.8 Hz, 1H), 5.64 (s, 1H), 4.61 (t, J=8.7 Hz, 2H), 3.29(m, 4H), 2.24 (q, J=7.5 Hz, 2H), 1.75 (m, 1H), 1.25 (m, 1H), 1.17 (t,J=7.5 Hz, 3H), 0.96 (m, 2H).

¹³C-NMR (CDCl₃, 300 MHz) 174.2, 160.0, 139.3, 128.6, 126.4, 116.0,107.2, 71.5, 44.0, 30.2, 29.0, 22.1, 20.1, 13.9, 10.3.

1-10. (canceled)
 11. Process for the preparation of a compoundcorresponding to the following formula (I-A)

in which: X represents a substituted boron atom chosen from the groupcomprising B(OH)₂, B(OR)₂, BF₃M, B(OR′)₃M in which: R is an alkyl groupcomprising 1 to 14 carbon atoms or an aryl group, optionallysubstituted, or is such that (OR)₂ forms a ring between the two oxygenatoms, (OR)₂ being in particular chosen from the group comprising thebivalent radicals deriving from diols, such as O—CH₂—CH₂—O,O—CH₂—CH₂—CH₂—O, O—CH₂—C(CH₃)₂—CH₂—O, O—C(CH₃)₂—CH₂—CH₂—C(CH₃)₂—O,O—CH(CH₃)—CH₂—CH₂—CH(CH₃)—O, O—CH(Ph)-CH(Ph)-O, O—CH(CH₃)—CH₂—C(CH₃)₂—O,O-o-Ph-O, O—CH₂—CH₂—NH—CH₂—CH₂—O,O—CH₂—CH₂—N(CH₂—CH₂—CH₂—CH₃)—CH₂—CH₂—O, O—CH(COOH)—CH(COOH)—O and itsesters, and the bivalent radicals deriving from diacids, such asOCO—CH₂—N(CH₃)—CH₂—COO, R′ is an alkyl group comprising 1 to 14 carbonatoms or is such that: (OR′)₃ forms a ring between two of the oxygenatoms, (OR′)₃ then being in the form OR′ (OR)₂, where R′ is an alkylgroup comprising 1 to 14 carbon atoms and (OR)₂ is as defined above, or(OR′)₃ forms a bicycle between the three oxygen atoms, (OR′)₃ being inparticular chosen from the group comprising the trivalent radicalsderiving from triols, such as H₂C—C—(CH₂—O)₃, M represents the lithiumLi⁺ ion, the sodium Na⁺ ion, the potassium K⁺ ion, the caesium Cs⁺ ion,the ammonium R^(c)R^(d)R^(e)R^(f)N⁺ ion where R^(c), R^(d) R^(e), R^(f)are chosen from H or a saturated carbon-containing chain comprising inparticular 1 to 6 carbon atoms chosen independently of one another, andin particular X represents B(OH)₂, B(OR)₂ or BF₃K, R₁ and R₄, identicalor different, are chosen from the group constituted by:
 1. H
 2. thearyls comprising rings with 6 to 15 carbon atoms, optionally substitutedby: one or more halogen atoms comprising fluorine, chlorine, bromine oriodine, hydroxy, amino or thio radicals optionally protected by “ad hoc”protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, alkylradicals with 1 to 15 carbon atoms, optionally substituted, alkenylradicals with 1 to 15 carbon atoms, optionally substituted, alkynylradicals with 1 to 15 carbon atoms, optionally substituted, aryls with 6to 12 carbon atoms, optionally substituted, aromatic or non-aromaticheterocycles with 2 to 12 carbon atoms, optionally substituted, in whichR^(a) and R^(b), identical or different, represent linear, cyclic orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted by: one or more halogen atoms comprising fluorine, chlorine,bromine or iodine, hydroxy, amino or thio radicals optionally protectedby “ad hoc” protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a),—OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN,—COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a),—N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a),—N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b)radicals, in which R^(a) and R^(b), identical or different, representlinear or branched, aromatic, or aromatic or non-aromatic heterocyclicalkyl, alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, alkylradicals comprising 1 to 15 carbon atoms, linear or branched optionallysubstituted, by the linear or branched alkenyl radicals comprising 1 to15 carbon atoms, optionally substituted, by the alkynyl radicalscomprising 1 to 15 carbon atoms, linear or branched optionallysubstituted, by the aryls with 6 to 12 carbon atoms, optionallysubstituted, by the aromatic or non-aromatic heterocycles comprising 2to 12 carbon atoms, optionally substituted,
 3. the heterocycles orheteroaryls comprising rings with 2 to 15 carbon atoms, optionallysubstituted by: one or more halogen atoms comprising fluorine, chlorine,bromine or iodine, by the hydroxy, amino or thio radicals optionallyprotected by “ad hoc” protective groups, —OR^(a), —NHR^(a),—NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO,—COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂,—N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a),—N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, by the alkyl radicals comprising 1to 15 carbon atoms, optionally substituted, by the linear or branchedalkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, by the linear or branched alkynyl radicals comprising 1 to15 carbon atoms, optionally substituted, by the linear or branched arylradicals comprising 6 to 12 carbon atoms, optionally substituted, by thearomatic or non-aromatic heterocycles comprising 2 to 12 carbon atoms,optionally substituted, in which R^(a) and R^(b), identical ordifferent, represent linear, cyclic or branched, aromatic, or aromaticor non-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1to 15 carbon atoms, optionally substituted by: one or more halogen atomscomprising fluorine, chlorine, bromine or iodine, hydroxy, amino or thioradicals optionally protected by “ad hoc” protective groups, —OR^(a),—NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyls, alkenyl, alkynyls groups comprising 1to 15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms,optionally substituted, linear or branched alkenyl radicals comprising 1to 15 carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, aromatic or non-aromatic heterocycles comprising 2 to 12carbon atoms, optionally substituted,
 4. the linear or branched alkenylscomprising 1 to 12 carbon atoms, optionally substituted, or carbon ringscomprising 3 to 12 carbon atoms and one or more C═C double bonds,optionally substituted by: one or more halogen atoms comprisingfluorine, chlorine, bromine or iodine, by the hydroxy, amino or thioradicals optionally protected by “ad hoc” protective groups, —OR^(a),—NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, by the alkyl radicals comprising 1to 15 carbon atoms, optionally substituted, by the linear or branchedalkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, by the linear or branched alkynyl radicals comprising 1 to15 carbon atoms, optionally substituted, by the linear or branched arylradicals comprising 6 to 12 carbon atoms, optionally substituted, by thearomatic or non-aromatic heterocycles comprising 2 to 12 carbon atoms,optionally substituted, in which R^(a) and R^(b), identical ordifferent, represent linear, cyclic or branched, aromatic, or aromaticor non-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1to 15 carbon atoms, optionally substituted by: one or more halogen atomscomprising fluorine, chlorine, bromine or iodine, by the hydroxy, aminoor thio radicals optionally protected by “ad hoc” protective groups,—OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl, groups comprising 1to 15 carbon atoms, by the alkyl radicals comprising 1 to 15 carbonatoms, optionally substituted, by the linear or branched alkenylradicals comprising 1 to 15 carbon atoms, optionally substituted, by thelinear or branched alkynyl radicals comprising 1 to 15 carbon atoms,optionally substituted, by the linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, by the aromaticor non-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted,
 5. the linear or branched alkynyls comprising 1 to 15carbon atoms, optionally substituted by: one or more halogen atomscomprising fluorine, chlorine, bromine or iodine, by the hydroxy, aminoor thio radicals optionally protected by “ad hoc” protective groups,—OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₂, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, by the alkyl radicals comprising 1to 15 carbon atoms, optionally substituted, by the linear or branchedalkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, by the linear or branched alkynyl radicals comprising 1 to15 carbon atoms, optionally substituted, by the linear or branched arylradicals comprising 6 to 12 carbon atoms, optionally substituted, by thearomatic or non-aromatic heterocycles comprising 2 to 12 carbon atoms,optionally substituted, in which R^(a) and R^(b), identical ordifferent, represent linear, cyclic or branched, aromatic, or aromaticor non-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1to 15 carbon atoms, optionally substituted by: one or more halogen atomscomprising fluorine, chlorine, bromine or iodine, hydroxy, amino or thioradicals optionally protected by “ad hoc” protective groups, —OR^(a),—NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms,optionally substituted, linear or branched alkenyl radicals comprising 1to 15 carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, aromatic or non-aromatic heterocycles comprising 2 to 12carbon atoms, optionally substituted,
 6. linear, cyclic or branchedalkyl groups comprising 1 to 15 carbon atoms, optionally substituted by:one or more halogen atoms comprising fluorine, chlorine, bromine oriodine, hydroxy, amino or thio radicals optionally protected by “ad hoc”protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, alkylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, in which R^(a) and R^(b), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted by: one or more halogen atoms comprisingfluorine, chlorine, bromine or iodine, hydroxy, amino or thio radicalsoptionally protected by “ad hoc” protective groups, —OR^(a), —NHR^(a),—NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a), OCONR^(a)R^(b), —CHO,—COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂,—N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a),—N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms,optionally substituted, linear or branched alkenyl radicals comprising 1to 15 carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, aromatic or non-aromatic heterocycles comprising 2 to 12carbon atoms, optionally substituted, at least one of the R₁ and R₄groups representing H, R₂ is chosen from the group constituted by thegroups being able to be represented by R₁ or R₄, as well as —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂, in whichR^(a) and R^(b), identical or different, represent linear, cyclic orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted by: one or more halogen atoms comprising fluorine, chlorine,bromine or iodine, hydroxy, amino or thio radicals optionally protectedby “ad hoc” protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a),—OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN,—COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a),—N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a)) NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, inwhich R^(a) and R^(b), identical or different, represent linear orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, alkyl radicalscomprising 1 to 15 carbon atoms, optionally substituted, linear orbranched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, R^(a) and R^(b) being able to be linked in order to form aring, optionally substituted, W represents a functional group chosenfrom —CHO, —COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b), —CONH—SO₂—R^(a), —CH₂OH, —CH₂OR^(a), —CHR^(b)OH,—CHR^(b)OR^(a), —CR^(b)R^(b′)OH, —CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ,—CHR^(a)NHZ, —CH₂—NH—COR^(a), in which Z represents a protective groupof an amine function, and in which R^(a), R^(b) and R^(b′), identical ordifferent, represent linear, cyclic or branched, aromatic, or aromaticor non-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1to 15 carbon atoms, optionally substituted by: one or more halogen atomscomprising fluorine, chlorine, bromine or iodine, hydroxy, amino or thioradicals optionally protected by “ad hoc” protective groups, —OR^(a),—NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms,optionally substituted, linear or branched alkenyl radicals comprising 1to 15 carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, aromatic or non-aromatic heterocycles comprising 2 to 12carbon atoms, optionally substituted, said process comprising: a step ofreaction between: a diazoic derivative of the following formula:

in which R₂ is as defined above, W₁ being chosen from the groupconstituted by —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a), and—CONR^(a)R^(b), and a vinyltrifluoroborate compound of the followingformula:

in which R₁, R₄ and M are as defined above, in the presence of acatalyst containing a transition metal, in order to obtain a compound ofthe following formula:

in which R₁, R₂, R₄, W₁ and M are as defined above, if W is differentfrom W₁ and/or X is different from MF₃B, said process also comprisingthe following steps: a step of conversion of W₁ to W making it possibleto obtain

in particular, when W₁=COOR^(a) and W=CHO, by reduction in order to formthe corresponding alcohol, then oxidation of said alcohol, whenW₁=—COOR^(a) and W=CH₂OH or —CH₂OR^(b), by the formation of an aldehydeas described previously, then by reduction of said aldehyde and optionalalkylation, when W₁=—COR^(a) and W=—CHR^(a)OH, —CHR^(a)OR^(b), byreduction then optional alkylation of the alcohol obtained, whenW₁=—COR^(a) and W=CR^(a)R^(b)OH or —CR^(a)R^(b)OR^(b′) by addition of aGrignard reagent then optional alkylation of the alcohol obtained, whenW₁=—CONH₂, —CONHR^(a) or —CONR^(a)R^(b) and W=—CH₂NH₂, —CH₂NHR^(a),—CH₂NR^(a)R^(b), —CH₂NHZ or —CH₂—NH—COR^(a), by reduction then optionalprotection by Z of the amine obtained or optional reaction with the acidchloride R^(a)COCl, when W₁=—CONH₂ and W=—CONHSO₂R^(a), by the action ofsulphonyl chloride ClSO₂R^(a) on the amide, and a step of conversion of—BF₃M to —X making it possible to obtain

in particular, when X=B(OH)₂, by basic or acid hydrolysis, or by passingvia a dihalogenoborane, more particularly a dichloroborane, whenX=B(OR)₂, by passing via X=B(OH)₂ as described previously then by theaction of an alcohol, in particular an alcohol of formula ROH, a diol ora triol, or by passing via a dihalogenoborane, more particularly adichloroborane, then by the action of an alcohol, in particular analcohol of formula ROH, a diol or a triol, or a step of conversion of—BF₃M to —X making it possible to obtain

and a step of conversion of W₁ to W making it possible to obtain


12. Process according to claim 11, in which said catalyst containing atransition metal, said catalyst being in particular a palladium (II)complex, more particularly Pd(OAc)₂ or Pd(acac)₂, a copper (II) complex,more particularly CuSO₄, Cu(acac)₂, Cu(tBuSalen)₂, Cu(OTf)₂, a copper(I) complex, more particularly CuI or Cu(OTf), or a rhodium (II)complex, more particularly Rh₂(OAc)₄, Rh₂(Octanoate)₄ or Rh₂(5S-MEPY)₄(Doyle catalyst).
 13. Process according to claim 11, in which W₁represents —COOR^(a), R^(a) being as defined previously, in particularin which W represents —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b),—CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, said processcomprising: a step of reaction between: a diazoic derivative of thefollowing formula:

in which R^(a) is as defined previously, and a vinyltrifluoroboratecompound of the following formula:

in which M is as defined previously, M representing in particular K, inthe presence of a catalyst containing a transition metal, in order toobtain a compound of the following formula:

in which R^(a) and M are as defined above, if W is different from—COOR^(a) and/or X is different from MF₃B, said process also comprisingthe following steps: a step of conversion of —COOR^(a) to W making itpossible to obtain

and a step of conversion of —BF₃M to —X making it possible to obtain

or a step of conversion of —BF₃M to —X making it possible to obtain

and a step of conversion of —COOR^(a) to W making it possible to obtain


14. Process according to claim 11, in which: R₂ is chosen from the groupconstituted by the —COR^(a), —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b), —CN and —NO₂ groups, in which R^(a) and R^(b), identicalor different, represent linear, cyclic or branched, aromatic, oraromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted by: one or morehalogen atoms comprising fluorine, chlorine, bromine or iodine, hydroxy,amino or thio radicals optionally protected by “ad hoc” protectivegroups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH) NH₂,—N—(C═NCOR^(a)) NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, in whichR^(a) and R^(b), identical or different, represent linear or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, alkyl radicalscomprising 1 to 15 carbon atoms, optionally substituted, linear orbranched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, R^(a) and R^(b) being able to be linked in order to form aring, optionally substituted, or in which R₂ represents H, or in whichR₁, R₂ and R₄ represent H, or in which R₁ represents H, or in which R₁represents H and R₄ represents an aryl, a heterocycle, a heteroaryl oran alkyl as defined previously, or in which R₄ represents H, or in whichR₄ represents H and R₁ represents an aryl, a heterocycle, a heteroarylor an alkyl as defined previously, or in which R₁ and R₂ represent H andR₄ represents an aryl, a heterocycle, a heteroaryl or an alkyl asdefined previously, or in which R₂ and R₄ represent H and R₁ representsan aryl, a heterocycle, a heteroaryl or an alkyl as defined previously.15. Process according to claim 11, in which W represents a functionalgroup chosen from —CONH—SO₂-cyclopropyl, —CH₂—NH—CO—CH₂—CH₃, and thegroup of the following formula:


16. Compound corresponding to the following formula (I-A)

in which: X represents a substituted boron atom chosen from the groupcomprising B(OH)₂, B(OR)₂, BF₃M, B(OR′)₃M in which: R is an alkyl groupcomprising 1 to 14 carbon atoms, an aryl group, optionally substituted,or is such that (OR)₂ forms a ring between the two oxygen atoms, (OR)₂being in particular chosen from the group comprising the bivalentradicals deriving from diols, such as O—CH₂—CH₂—O, O—CH₂—CH₂—CH₂—O,O—CH₂—C(CH₃)₂—CH₂—O, O—C(CH₃)₂—CH₂—CH₂—C(CH₃)₂—O,O—CH(CH₃)—CH₂—CH₂—CH(CH₃)—O, O—CH(Ph)-CH(Ph)-O, O—CH(CH₃)—CH₂—C(CH₃)₂—O,O-o-Ph-O, O—CH₂—CH₂—NH—CH₂—CH₂—O,O—CH₂—CH₂—N(CH₂—CH₂—CH₂—CH₃)—CH₂—CH₂—O, O—CH(COOH)—CH(COOH)—O and itsesters, and the bivalent radicals deriving from diacids, such asOCO—CH₂—N(CH₃)—CH₂—COO, R′ is an alkyl group comprising 1 to 14 carbonatoms or is such that: (OR′)₃ forms a ring between two of the oxygenatoms, (OR′)₃ then being in the form OR′ (OR)₂, where R′ is an alkylgroup comprising 1 to 14 carbon atoms and (OR)₂ is as defined above, or(OR′)₃ forms a bicycle between the three oxygen atoms, (OR′)₃ being inparticular chosen from the group comprising the trivalent radicalsderiving from triols, such as H₃C—C—(CH₂—O)₃, M represents the lithiumLi⁺ ion, the sodium Na⁺ ion, the potassium K⁺ ion, the caesium Cs⁺ ion,the ammonium R^(c)R^(d)R^(e)R^(f)N⁺ ion where R^(c), R^(d) R^(e), R^(f)are chosen from H or a saturated carbon-containing chain comprising inparticular 1 to 6 carbon atoms chosen independently of one another, andin particular X represents B(OH)₂, B(OR)₂ or BF₃K, R₁ and R₄, identicalor different, are chosen from the group constituted by:
 1. H
 2. thearyls comprising rings with 6 to 15 carbon atoms, optionally substitutedby: one or more halogen atoms comprising fluorine, chlorine, bromine oriodine, by the hydroxy, amino or thio radicals optionally protected by“ad hoc” protective groups, —OR^(d), —NHR^(d), —NR^(a)R^(b), —SR^(d),—OCOR^(d), —OCONHR^(d), —OCONR^(a)R^(b), —CHO, —COR^(d), —COOH, —CN,—COOR^(d), —CONHR^(d), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(d),—N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(d), —N═C—NH—COOR^(d),—N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b)radicals, by the alkyl radicals with 1 to 15 carbon atoms, optionallysubstituted, by the alkenyl radicals with 1 to 15 carbon atoms,optionally substituted, by the alkynyl radicals with 1 to 15 carbonatoms, optionally substituted, by the aryls with 6 to 12 carbon atoms,optionally substituted, by the aromatic or non-aromatic heterocycleswith 2 to 12 carbon atoms, optionally substituted, in which R^(a) andR^(b), identical or different, represent linear, cyclic or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, optionally substitutedby: one or more halogen atoms comprising fluorine, chlorine, bromine oriodine, hydroxy, amino or thio radicals optionally protected by “ad hoc”protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, in whichR^(a) and R^(b), identical or different, represent linear or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, linear or branched alkylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, aryls with 6 to 12 carbon atoms,optionally substituted, aromatic or non-aromatic heterocycles comprising2 to 12 carbon atoms, optionally substituted,
 3. the heterocycles orheteroaryls comprising rings with 2 to 15 carbon atoms, optionallysubstituted by: one or more halogen atoms comprising fluorine, chlorine,bromine or iodine, hydroxy, amino or thio radicals optionally protectedby “ad hoc” protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a),—OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN,—COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a),—N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a),—N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b)radicals, alkyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkenyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, aromatic or non-aromatic heterocycles comprising 2 to 12carbon atoms, optionally substituted, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted by: one or morehalogen atoms comprising fluorine, chlorine, bromine or iodine, hydroxy,amino or thio radicals optionally protected by “ad hoc” protectivegroups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, in whichR^(a) and R^(b), identical or different, represent linear or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, alkyl radicalscomprising 1 to 15 carbon atoms, optionally substituted, linear orbranched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted,
 4. the linear or branched alkenyls comprising 1 to 12carbon atoms, optionally substituted, or carbon rings comprising 3 to 12carbon atoms and one or more C═C double bonds, optionally substitutedby: one or more halogen atoms comprising fluorine, chlorine, bromine oriodine, hydroxy, amino or thio radicals optionally protected by “ad hoc”protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, alkylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, in which R^(a) and R^(b), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted by: one or more halogen atoms comprisingfluorine, chlorine, bromine or iodine, hydroxy, amino or thio radicalsoptionally protected by “ad hoc” protective groups, —OR^(a), —NHR^(a),—NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO,—COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂,—N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a),—N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms,optionally substituted, linear or branched alkenyl radicals comprising 1to 15 carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, aromatic or non-aromatic heterocycles comprising 2 to 12carbon atoms, optionally substituted,
 5. the linear or branched alkynylscomprising 1 to 15 carbon atoms, optionally substituted by: one or morehalogen atoms comprising fluorine, chlorine, bromine or iodine, hydroxy,amino or thio radicals optionally protected by “ad hoc” protectivegroups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, alkylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, in which R^(a) and R^(b), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted by: one or more halogen atoms comprisingfluorine, chlorine, bromine or iodine, hydroxy, amino or thio radicalsoptionally protected by “ad hoc” protective groups, —OR^(a), —NHR^(a),—NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO,—COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₂, —NO₂,—N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a),—N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms,optionally substituted, linear or branched alkenyl radicals comprising 1to 15 carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, aromatic or non-aromatic heterocycles comprising 2 to 12carbon atoms, optionally substituted,
 6. the linear, cyclic or branchedalkyl groups comprising 1 to 15 carbon atoms, optionally substituted by:one or more halogen atoms comprising fluorine, chlorine, bromine oriodine, hydroxy, amino or thio radicals optionally protected by “ad hoc”protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, alkylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, in which R^(a) and R^(b), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted by: one or more halogen atoms comprisingfluorine, chlorine, bromine or iodine, hydroxy, amino or thio radicalsoptionally protected by “ad hoc” protective groups, —OR^(a), —NHR^(a),—NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO,—COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂,—N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a),—N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms,optionally substituted, linear or branched alkenyl radicals comprising 1to 15 carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, aromatic or non-aromatic heterocycles comprising 2 to 12carbon atoms, optionally substituted, at least one of the R₁ and R₄groups representing H, R₂ is chosen from the group constituted by thegroups being able to be represented by R₁ or R₄, as well as —COR^(a),—COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂, in whichR^(a) and R^(b), identical or different, represent linear, cyclic orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, optionallysubstituted by: one or more halogen atoms comprising fluorine, chlorine,bromine or iodine, hydroxy, amino or thio radicals optionally protectedby “ad hoc” protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a),—OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN,—COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a),—N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, inwhich R^(a) and R^(b), identical or different, represent linear orbranched, aromatic, or aromatic or non-aromatic heterocyclic alkyl,alkenyl, alkynyl groups comprising 1 to 15 carbon atoms, alkyl radicalscomprising 1 to 15 carbon atoms, optionally substituted, linear orbranched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, R^(a) and R^(b) being able to be linked in order to form aring, optionally substituted, W represents a functional group chosenfrom —CHO, —COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b), —CONH—SO₂—R^(a), —CH₂OH, —CH₂OR^(a), —CHR^(b)OH,—CHR^(b)OR^(a), —CR^(b)R^(b′)OH, —CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ,—CHR^(a)NHZ, —CH₂—NH—COR^(a), in which Z represents a protective groupof an amine function, and in which R^(a), R^(b) and R^(b′), identical ordifferent, represent linear, cyclic or branched, aromatic, or aromaticor non-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1to 15 carbon atoms, optionally substituted by: one or more halogen atomscomprising fluorine, chlorine, bromine or iodine, hydroxy, amino or thioradicals optionally protected by “ad hoc” protective groups, —OR^(a),—NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms,optionally substituted, linear or branched alkenyl radicals comprising 1to 15 carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, by the aromatic or non-aromatic heterocycles comprising 2to 12 carbon atoms, optionally substituted, provided that: when R₁, R₂and R₄ represent H and B represents B(OH)_(2r) B(OR)₂, or B(OR′)₃M, thenW is chosen from —COR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), when R₁,R₂ and R₄ represent H and B represents BF₃M, then W is chosen from—COOH, —COOR^(a), —CHO, —COR^(a)—CONH₂, —CONHR^(a), —CONR^(a)R^(b), whenW represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),—CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents B(OH)_(2r)B(OR)₂, or B(OR′)₃M, then: R₁ does not represent H, or R₂ and R₄ do notrepresent H, when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH,—CHR^(b)OR^(a), —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and Brepresents BF₃M, then R₁ or R₂ does not represent H. when W represents—COOH or —COOR^(a), and B represents B(OH)₂, B(OR)₂, or B(OR′)₃M, then:R₁ does not represent H, or R₂ and R₄ do not represent H.
 17. Compoundaccording to claim 16, in which W represents a functional group chosenfrom —CHO, —COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b), —CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),—CR^(b)R^(b′)OH, —CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ, —CHR^(a)NHZ, inparticular in which W represents a functional group chosen from —CHO,—COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a), —CONR^(a)R^(b), —CH₂OH,—CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a), —CR^(b)R^(b′)OH,—CR^(b)R^(b′)OR^(a), more particularly in which W represents afunctional group chosen from —CHO, —COR^(a), —COOH, —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b). in particular in which W represents afunctional group chosen from —CONH—SO₂-cyclopropyl, —CH₂—NH—CO—CH₂—CH₃′and the group of the following formula:

in particular in which R₂ represents H, in particular in which R₂ ischosen from the group constituted by the —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂ groups, in which R^(a) andR^(b), identical or different, represent linear, cyclic or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, optionally substitutedby: one or more halogen atoms comprising fluorine, chlorine, bromine oriodine, hydroxy, amino or thio radicals optionally protected by “ad hoc”protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH) NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, in whichR^(a) and R^(b), identical or different, represent linear or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, alkyl radicalscomprising 1 to 15 carbon atoms, optionally substituted, linear orbranched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, R^(a) and R^(b) being able to be linked in order to form aring, optionally substituted, in particular in which R₁ and R₄ representH, an aryl, a heterocycle, a heteroaryl or an alkyl as definedpreviously, in particular in which R₁, R₂ and R₄ represent H, inparticular in which R₁ represents H, in particular in which R₁represents H and R₄ represents an aryl, a heterocycle, a heteroaryl oran alkyl as defined previously, in particular in which R₄ represents H,in particular in which R₄ represents H and R1 represents an aryl, aheterocycle, a heteroaryl or an alkyl as defined previously, inparticular in which R₁ and R₂ represent H and R₄ represents an aryl, aheterocycle, a heteroaryl or an alkyl as defined previously, inparticular in which R₂ and R₄ represent H and R₁ represents an aryl, aheterocycle, a heteroaryl or an alkyl as defined in previously. 18.Compound according to claim 16, said compound being chosen from thegroup constituted by the compounds of the following formulae and theirenantiomers:


19. Method of preparation of compounds of the following formula (II-A):

in which: R₁, R₃ and R₄, identical or different, are chosen from thegroup constituted by:
 1. H, provided that R₃ does not represent H, 2.the aryls comprising rings with 6 to 15 carbon atoms, optionallysubstituted by: one or more halogen atoms comprising fluorine, chlorine,bromine or iodine, hydroxy, amino or thio radicals optionally protectedby “ad hoc” protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a),—OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN,—COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₂, —NO₂, —N═C—NHR^(a),—N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a),—N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b)radicals, alkyl radicals with 1 to 15 carbon atoms, optionallysubstituted, alkenyl radicals with 1 to 15 carbon atoms, optionallysubstituted, alkynyl radicals with 1 to 15 carbon atoms, optionallysubstituted, aryls with 6 to 12 carbon atoms, optionally substituted,aromatic or non-aromatic heterocycles with 2 to 12 carbon atoms,optionally substituted, in which R^(a) and R^(b), identical ordifferent, represent linear, cyclic or branched, aromatic, or aromaticor non-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1to 15 carbon atoms, optionally substituted by: one or more halogen atomscomprising fluorine, chlorine, bromine or iodine, hydroxy, amino or thioradicals optionally protected by “ad hoc” protective groups, —OR^(a),—NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms, linearor branched optionally substituted, linear or branched alkenyl radicalscomprising 1 to 15 carbon atoms, optionally substituted, linear orbranched alkynyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, aryls with 6 to 12 carbon atoms, optionally substituted,aromatic or non-aromatic heterocycles comprising 2 to 12 carbon atoms,optionally substituted,
 3. the heterocycles or heteroaryls comprisingrings with 2 to 15 carbon atoms, optionally substituted by: one or morehalogen atoms comprising fluorine, chlorine, bromine or iodine, hydroxy,amino or thio radicals optionally protected by “ad hoc” protectivegroups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, alkylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, in which R^(a) and R^(b), identical or different, representlinear, cyclic or branched, aromatic, or aromatic or non-aromaticheterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to 15 carbonatoms, optionally substituted by: one or more halogen atoms comprisingfluorine, chlorine, bromine or iodine, hydroxy, amino or thio radicalsoptionally protected by “ad hoc” protective groups, —OR^(a), —NHR^(a),—NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO,—COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂,—N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a),—N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms,optionally substituted, linear or branched alkenyl radicals comprising 1to 15 carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, aromatic or non-aromatic heterocycles comprising 2 to 12carbon atoms, optionally substituted,
 4. the linear or branched alkenylscomprising 1 to 12 carbon atoms, optionally substituted, or carbon ringscomprising 3 to 12 carbon atoms and one or more C═C double bonds,optionally substituted by: one or more halogen atoms comprisingfluorine, chlorine, bromine or iodine, hydroxy, amino or thio radicalsoptionally protected by “ad hoc” protective groups, —OR^(a), —NHR^(a),—NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a), —OCONR^(a)R^(b), —CHO,—COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂,—N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂, —N═C—NHCOR^(a),—N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, alkyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched alkenylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched alkynyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched aryl radicals comprising 6 to 12 carbonatoms, optionally substituted, aromatic or non-aromatic heterocyclescomprising 2 to 12 carbon atoms, optionally substituted, in which R^(a)and R^(b), identical or different, represent linear, cyclic or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, optionally substitutedby: one or more halogen atoms comprising fluorine, chlorine, bromine oriodine, hydroxy, amino or thio radicals optionally protected by “ad hoc”protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, in whichR^(a) and R^(b), identical or different, represent linear or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, alkyl radicalscomprising 1 to 15 carbon atoms, optionally substituted, linear orbranched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted,
 5. the linear or branched alkynyls comprising 1 to 15carbon atoms, optionally substituted by: one or more halogen atomscomprising fluorine, chlorine, bromine or iodine, hydroxy, amino or thioradicals optionally protected by “ad hoc” protective groups, —OR^(a),—NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, alkyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched alkenylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched alkynyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched aryl radicals comprising 6 to 12 carbonatoms, optionally substituted, aromatic or non-aromatic heterocyclescomprising 2 to 12 carbon atoms, optionally substituted, in which R^(a)and R^(b), identical or different, represent linear, cyclic or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, optionally substitutedby: one or more halogen atoms comprising fluorine, chlorine, bromine oriodine, hydroxy, amino or thio radicals optionally protected by “ad hoc”protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, in whichR^(a) and R^(b), identical or different, represent linear or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, alkyl radicalscomprising 1 to 15 carbon atoms, optionally substituted, linear orbranched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted,
 6. the linear, cyclic or branched alkyl groups comprising 1to 15 carbon atoms, optionally substituted by: one or more halogen atomscomprising fluorine, chlorine, bromine or iodine, hydroxy, amino or thioradicals optionally protected by “ad hoc” protective groups, —OR^(a),—NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, alkyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched alkenylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched alkynyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched aryl radicals comprising 6 to 12 carbonatoms, optionally substituted, aromatic or non-aromatic heterocyclescomprising 2 to 12 carbon atoms, optionally substituted, in which R^(a)and R^(b), identical or different, represent linear, cyclic or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, optionally substitutedby: one or more halogen atoms comprising fluorine, chlorine, bromine oriodine, hydroxy, amino or thio radicals optionally protected by “ad hoc”protective groups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, in whichR^(a) and R^(b), identical or different, represent linear or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, alkyl radicalscomprising 1 to 15 carbon atoms, optionally substituted, linear orbranched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, at least one of the R₁ and R₄ groups representing H, R₂ ischosen from the group constituted by the groups being able to berepresented by R₁ or R₄, as well as —COR^(a), —COOR^(a), —CONH₂,—CONHR^(a), —CONR^(a)R^(b), —CN and —NO₂, in which R^(a) and R^(b),identical or different, represent linear, cyclic or branched, aromatic,or aromatic or non-aromatic heterocyclic alkyl, alkenyl, alkynyl groupscomprising 1 to 15 carbon atoms, optionally substituted by: one or morehalogen atoms comprising fluorine, chlorine, bromine or iodine, hydroxy,amino or thio radicals optionally protected by “ad hoc” protectivegroups, —OR^(a), —NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a),—OCONHR^(a), —OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a),—CONHR^(a), —CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b),—N═C—NH₂, —N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH) NH₂,—N—(C═NCOR^(a))NHCOR^(b), —N(C═NCOOR^(a))NHCOOR^(b) radicals, in whichR^(a) and R^(b), identical or different, represent linear or branched,aromatic, or aromatic or non-aromatic heterocyclic alkyl, alkenyl,alkynyl groups comprising 1 to 15 carbon atoms, alkyl radicalscomprising 1 to 15 carbon atoms, optionally substituted, linear orbranched alkenyl radicals comprising 1 to 15 carbon atoms, optionallysubstituted, linear or branched alkynyl radicals comprising 1 to 15carbon atoms, optionally substituted, linear or branched aryl radicalscomprising 6 to 12 carbon atoms, optionally substituted, aromatic ornon-aromatic heterocycles comprising 2 to 12 carbon atoms, optionallysubstituted, R^(a) and R^(b) being able to be linked in order to form aring, optionally substituted, W represents a functional group chosenfrom —CHO, —COR^(a), —COOH, —COOR^(a), —CONH₂, —CONHR^(a),—CONR^(a)R^(b), —CONH—SO₂—R^(a), —CH₂OH, —CH₂OR^(a), —CHR^(b)OH,—CHR^(b)OR^(a), —CR^(b)R^(b′)OH, —CR^(b)R^(b′)OR^(a), —CH₂NH₂, —CH₂NHZ,—CHR^(a)NHZ, —CH₂—NH—COR^(a), in which Z represents a protective groupof an amine function, and in which R^(a), R^(b) and R^(b′), identical ordifferent, represent linear, cyclic or branched, aromatic, or aromaticor non-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1to 15 carbon atoms, optionally substituted by: one or more halogen atomscomprising fluorine, chlorine, bromine or iodine, hydroxy, amino or thioradicals optionally protected by “ad hoc” protective groups, —OR^(a),—NHR^(a), —NR^(a)R^(b), —SR^(a), —OCOR^(a), —OCONHR^(a),—OCONR^(a)R^(b), —CHO, —COR^(a), —COOH, —CN, —COOR^(a), —CONHR^(a),—CONR^(a)R^(b), —CF₃, —NO₂, —N═C—NHR^(a), —N═C—NR^(a)R^(b), —N═C—NH₂,—N═C—NHCOR^(a), —N═C—NH—COOR^(a), —N(C═NH)NH₂, —N—(C═NCOR^(a))NHCOR^(b),—N(C═NCOOR^(a))NHCOOR^(b) radicals, in which R^(a) and R^(b), identicalor different, represent linear or branched, aromatic, or aromatic ornon-aromatic heterocyclic alkyl, alkenyl, alkynyl groups comprising 1 to15 carbon atoms, alkyl radicals comprising 1 to 15 carbon atoms,optionally substituted, linear or branched alkenyl radicals comprising 1to 15 carbon atoms, optionally substituted, linear or branched alkynylradicals comprising 1 to 15 carbon atoms, optionally substituted, linearor branched aryl radicals comprising 6 to 12 carbon atoms, optionallysubstituted, aromatic or non-aromatic heterocycles comprising 2 to 12carbon atoms, optionally substituted, provided that: when R₁, R₂ and R₄represent H and B represents B(OH)₂, B(OR)₂, or B(OR′)₃M, then W ischosen from —COR^(a), —CONH₂, —CONHR^(a), and —CONR^(a)R^(b), when R₁,R₂ and R₄ represent H and B represents BF₃M, then W is chosen from—COOH, —COOR^(a), —CHO, —COR^(a)—CONH₂, —CONHR^(a), —CONR^(a)R^(b), whenW represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH, —CHR^(b)OR^(a),—CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and B represents B(OH)₂,B(OR)₂, or B(OR′)₃M, then: R₁ does not represent H, or R₂ and R₄ do notrepresent H, when W represents CH₂OH, —CH₂OR^(a), —CHR^(b)OH,—CHR^(b)OR^(a), —CR^(b)R^(b′)OH, or —CR^(b)R^(b′)OR^(a), and Brepresents BF₃M, then R₁ or R₂ do not represent H. when W represents—COOH or —COOR^(a), and B represents B(OH)₂, B(OR)₂, or B(OR′)₃M, then:R₁ does not represent H, or R₂ and R₄ do not represent H, by reaction ofa compound of formula (I-A) according to claim 16 with a compound of thefollowing formula (III):R₃—X₂ in which R₃ is as defined above, and X₂ is chosen from the groupconstituted by the halides, in particular iodine, bromine and chlorine,and triflate (OTf), in the presence of a catalyst containing atransition metal, and, optionally, of a ligand.
 20. Method according toclaim 19, in which R₃ represents a group chosen from:


21. Process according to claim 13, in which W represents a functionalgroup chosen from —CONH—SO₂-cyclopropyl, —CH₂—NH—CO—CH₂—CH₂, and thegroup of the following formula:


22. Process according to claim 14, in which W represents a functionalgroup chosen from —CONH—SO₂-cyclopropyl, —CH₂—NH—CO—CH₂—CH₂, and thegroup of the following formula: